Optical recording medium

ABSTRACT

Phthalocyanine compounds represented by the below-described formula are suitable for use in the fabrication of color filters. ##STR1## wherein R 1 , R 4 , R 5 , R 8 , R 9 , R 12 , R 13  and R 16  represent a group represented by the below-described formula, H or a halogen atom, R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14  and R 15  represent an alkyl, alkoxyl, alkylthio, alkylamino, dialkylamino or aryloxyl, arylthio group or --COOR 17 , R 17  being a particular monovalent group, H or a halogen atom; and Met represents a metal atom. ##STR2## wherein X and Z represent O or S, R 18 , R 19  and R 20  represent H or an alkyl group, A, B and D represent a connecting group, n and l is an integer of 0-10, m, q, t, u, r and w are an integer of 0-2, and p is 0 or 1.

This application is a continuation of application Ser. No. 08/305,317, filed Sep. 15, 1994, now abandoned, which is a division of application Ser. No. 07/901,484 filed Jun. 22, 1992, now U.S. Pat. No. 5,380,842.

BACKGROUND OF THE INVENTION

1) Field of the Invention

This invention relates to green dyes, which can play an important role in color filters for display devices such as liquid crystal television sets or in color separation filters for image pickup tubes or color copying machines, and also to color filters. The present invention is also concerned with near infrared absorbers, which can play an important role in optoelectronics-related fields such as recording of information, image sensors and protective goggles, and also with optical recording media fabricated using the near infrared absorbers.

2) Description of the Related Art

Known conventional filters using a phthalocyanine compound include inter alia those disclosed in Japanese Patent Laid-Open Nos. 30509/1984, 249102/1985, 140902/1986, 254903/1986, 254904/1986, 6904/1989, 88505/1989 and 233401/1989.

Among such phthalocyanine compounds, water-soluble compounds containing one or more sulfonic groups are suited for coloring filters in which gelatin or casein is used as a base material, and have been employed in gelatin-base filters. These filters have, however, been used only to a limited extent due to the poor heat resistance and moisture resistance of the filters per se. The phthalocyanine compounds containing substituents at the β-positions thereof, which are disclosed in Japanese Patent Laid-Open No. 233401/1989, are excellent in durability but are not sufficient in transmission characteristics. On the other hand, phthalocyanine compounds containing substituents at the α-positions, which are disclosed in WO 88/06175 and GB 2168372A, are accompanied by the drawback that they have poor solubility in resins and, to obtain a color density useful as a green filter, the film thickness of the filter must be increased. Further, their transmittance characteristics as green dyes are not sufficient.

Usage of phthalocyanine compounds as near infrared absorbers is widely known, for example, from Japanese Patent Laid-Open Nos. 209583/1985, 152769/1986, 154888/1986, 197280/1986, 246091/1986 and 39286/1987. The absorption ability of these phthalocyanine compounds was however not sufficient as they are prone to association. Optical recording media making use of one or more of such phthalocyanine compounds are, therefore, accompanied by drawbacks such as low reflectance at 780-830 nm and insufficient sensitivity and recording characteristics.

SUMMARY OF THE INVENTION

An object of this invention is to improve the poor solubility in a binder resin, transmittance characteristics, light resistance and heat resistance, which are the drawbacks common to such conventional green filters as described above and also to such green filter dyes as referred to above.

Another object of this invention is to provide a novel near infrared absorber free of the above-mentioned drawbacks and also an optical recording medium fabricated using the novel near infrared absorber and having high reflectance and good sensitivity and recording characteristics.

A further object of this invention is to provide a near infrared absorber, which has high solubility in liquid crystal compounds employed in liquid crystal devices and also exhibits good sensitivity to laser beam writing.

The present inventors have conducted extensive research with a view toward attaining the above-objects. As a result, it has been found that the solubility in a resin can be improved by the use of a phthalocyanine compound substituted at the α-position thereof by particular substituents, preferably each substituent containing one or more hetero atoms, desirably one or more nitrogen atoms, thereby making it possible to obtain a filter having good transmittance characteristics and excellent durability such as heat resistance and light resistance. As reasons for the good transmittance characteristics of the phthalocyanine compounds with hetero-atom-containing substituents at the α-positions, it may be mentioned that the introduction of the hetero atom in the side chain makes the polarity of the dye similar to that of the resin and, as a result, the compatibility between the resin and the dye is improved and the dye is stably distributed as discrete molecules in the resin.

It has also been found that the phthalocyanine compounds substituted at the α-positions by N-containing substituents exhibit sharp absorption at 650-900 nm, have a high molecular absorption coefficient and are excellent as near infrared absorbers. Optical recording media making use of one or more of these near infrared absorbers have been found to have high reflectance and sensitivity in the near infrared range. As reasons for the good absorbing ability of the phthalocyanine compounds substituted at the α-positions by N-containing substituents, it can be mentioned that association of molecules is suppressed owing to the action of nitrogen atoms.

The present invention, therefore, provides a color filter and a near infrared absorber, both comprising a phthalocyanine compound represented by the following formula (I), and an optical recording medium and a liquid crystal display device, both fabricated using the same: ##STR3## wherein R¹, R⁴, R⁵, R⁸, R⁹, R¹², R¹³ and R¹⁶ independently represent a group represented by the below-described formula (II) or a hydrogen or halogen atom with the proviso that, in each of the combinations of R¹ and R⁴, R⁵ and R⁸, R⁹ and R¹², and R¹³ and R¹⁶, at least one of the groups is represented by the formula (II); R², R³, R⁶, R⁷, R¹⁰, R¹¹, R¹⁴ and R¹⁵ independently represent a substituted or unsubstituted C₁₋₂₀ alkyl, substituted or unsubstituted C₁₋₂₀ alkoxyl group, substituted or unsubstituted C₁₋₂₀ alkylthio, substituted or unsubstituted C₁₋₂₀ alkylamino, substituted or unsubstituted C₂₋₂₀ dialkylamino, substituted or unsubstituted aryloxyl, substituted or unsubstituted arylthio, --COOR¹⁷, R¹⁷ being a hydrogen atom or a substituted or unsubstituted alkyl group, hydroxyl or mercapto group or a halogen or hydrogen atom; and Met represents a metal atom. ##STR4## wherein X and Z represent an oxygen or sulfur atom, R¹⁸, R¹⁹ and R²⁰ independently represent a hydrogen atom or a substituted or unsubstituted C₁₋₂₀ alkyl group, A, B and D represent a connecting group, n and l stand for an integer of 0-10, m, q, t, u, r and w are an integer of 0-2, and p represents 0 or 1.

The present invention also provides a phthalocyanine compound represented by the following formula (III): ##STR5## wherein R²², R²⁵, R²⁶, R²⁹, R³⁰, R³³, R³⁴ and R³⁷ independently represent a group represented by the below-described formula (IV) or a hydrogen or halogen atom with the proviso that, in each of the combinations of R²² and R²⁵, R²⁶ and R²⁹, R³⁰ and R³³, and R³⁴ and R³⁷, at least one of the groups is represented by the formula (IV); R²³, R²⁴, R²⁷, R²⁸, R³¹, R³², R³⁵ and R³⁶ independently represent a substituted or unsubstituted C₁₋₂₀ alkyl, substituted or unsubstituted C₁₋₂₀ alkoxyl group, substituted or unsubstituted C₁₋₂₀ alkylthio, substituted or unsubstituted C₁₋₂₀ alkylamino, substituted or unsubstituted C₂₋₂₀ dialkylamino, substituted or unsubstituted aryloxyl, substituted or unsubstituted arylthio, --COOR³⁸, R³⁸ being a hydrogen atom or a substituted or unsubstituted alkyl group, hydroxyl or mercapto group or a halogen or hydrogen atom; and Met represents a metal atom; said formula (IV) being a group of the formula ##STR6## wherein X² and Z² represent an oxygen or sulfur atom, R³⁹, R⁴⁰ and R⁴¹ independently represent a hydrogen atom or a substituted or unsubstituted C₁₋₂₀ alkyl group, A², B² and D² represent a connecting group, n² and l² stand for an integer of 0-10, m² represents an integer of 0-3, r² and q² represent an integer of 0-2, u² is an integer of 1-2, t² is an integer of 1-3, and p² represents 0 or 1. In one embodiment, q², u², m², and t² are 1, r² is 0, A² is ##STR7## B² is --U⁵ --(CH₂)_(c) --, --V⁵ -- CH(CH₃)CH₂ !-- or --W⁵ -- CH₂ CH(CH₃)!--, --U⁵ --, --V⁵ -- and --W⁵ -- independently representing an oxygen or sulfur atom and c being an integer of 1-3, and D² is --C(R⁴²)H--, R⁴² representing a hydrogen atom or a substituted or unsubstituted alkyl group.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 through FIG. 3 illustrate fabrication steps of a color filter according to the present invention, in which FIG. 1 shows a substrate coated with a photosensitive resin containing a phthalocyanine compound of this invention, FIG. 2 illustrates an exposure step to light through a mask pattern, and FIG. 3 depicts a monochromatic color filter from which unexposed areas have been removed by development;

FIG. 4 is a cross-section of a trichromatic color filter; and

FIGS. 5 through 9 show transmittance spectra of color filters, respectively, in which FIG. 5 depicts a transmittance spectrum of a color filter containing the phthalocyanine compound of Example 1, FIG. 6 a transmittance spectrum of a color filter containing the phthalocyanine compound of Example 2, FIG. 7 a transmittance spectrum of a color filter containing the phthalocyanine compound of Example 3, FIG. 8 a transmittance spectrum of a color filter containing the phthalocyanine compound of Comparative Example 1, and FIG. 9 a transmittance spectrum of a color filter containing the phthalocyanine compound of Comparative Example 2.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Preferred embodiments of this invention will hereinafter be described.

In the formula (I), examples of the unsubstituted C₁₋₂₀ alkyl group represented by R², R³, R⁶, R⁷, R¹⁰, R¹¹, R¹⁴ or R¹⁵ include linear, branched and cyclic alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-dodecyl, cyclopentyl, cyclohexyl, n-heptyl, n-octyl, and n-nonyl.

Exemplary substituted C₁₋₂₀ alkyl groups include alkylalkyl groups such as isopropyl, iso-butyl, sec-butyl, t-butyl, iso-pentyl, neo-pentyl, 1,2-dimethylpropyl, 2-methylbutyl, 2-methylpentyl, 1,3-dimethylbutyl, 1-iso-propylpropyl, 1,2-dimethylbutyl, 1,4-dimethylpentyl, 2-methyl-1-iso-propylpropyl, 1-ethyl-3-methylbutyl, 2-ethylhexyl, 3-methyl-1-iso-propylbutyl and 2,2-dimethyl-1-iso-propyl-1-t-butylpropyl; alkoxyalkyl groups such as methoxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, γ-methoxypropyl, γ-ethoxypropyl, methoxyethoxyethyl, ethoxyethoxyethyl, dimethoxymethyl, diethoxymethyl, dimethoxyethyl, and diethoxyethyl; halogenated alkyl groups such as chloromethyl, 2,2,2-trichloroethyl, trifluoromethyl and 1,1,1,3,3,3-hexafluoro-2-propyl; and hydroxyalkyl groups such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl and hydroxyoctyl.

Examples of the substituted or unsubstituted C₁₋₂₀ alkoxy group include unsubstituted alkoxyl groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, t-butoxy, n-pentoxy, iso-pentoxy, neo-pentoxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy and n-decyloxy; alkylalkoxyl groups such as 1,2-dimethylpropoxy, 1,3-dimethylbutoxy, 1-iso-propylpropoxy, 1,2-dimethylbutoxy, 1,4-dimethylpentyloxy, 2-methyl-1-iso-propylpropoxy, 1-ethyl-3-methylbutoxy, 2-ethylhexyloxy, 3-methyl-1-iso-propylbutoxy, 2-methyl-1-iso-propylbutoxy and 1-t-butyl-2-methylpropoxy; alkoxyalkoxyl groups such as methoxymethoxy, methoxyethoxy, ethoxyethoxy, propoxyethoxy, butoxyethoxy, methoxypropoxy, γ-ethoxypropoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, dimethoxymethoxy, diethoxymethoxy, dimethoxyethoxy, and diethoxyethoxy; halogenated alkoxyl groups such as chloromethoxy, 2,2,2-trichloroethoxy, trifluoromethoxy, and 1,1,1,3,3,3-hexafluoro-2-propoxy; and hydroxyalkoxyl groups such as hydroxymethoxy, hydroxyethoxy, hydroxypropoxy, hydroxybutoxy, hydroxypentyloxy, and hydroxyoctyloxy,

Examples of the unsubstituted C₁₋₂₀ alkylthio group include methylthio, ethylthio, n-propylthio, propylthio, n-butylthio, iso-butylthio, sec-butylthio, t-butylthio, n-pentylthio, iso-pentylthio, neo-pentylthio, 1,2-dimethylpropylthio, n-hexylthio, cyclohexylthio, 1,3-dimethylbutylthio, 1-iso-propylpropylthio, 1,2-dimethylbutylthio, n-heptylthio, 1,4-dimethylpentylthio, 2-methyl-1-iso-propylpropylthio, 1-ethyl-3-methylbutylthio, n-octylthio, 2-ethylhexylthio, 3-methyl-1-iso-propylbutylthio, 2-methyl-1-iso-propylbutylthio, 1-t-butyl-2-methylpropylthio, n-nonylthio and n-decylthio groups. Exemplary substituted alkylthio groups include alkylthioalkylthio groups such as methylthiomethylthio, methylthioethylthio, ethylthioethylthio, propylthioethylthio; halogenated alkylthio groups such as chloromethylthio, 2,2,2-trichloroethylthio, trifluoromethylthio, 1,1,1,3,3,3-hexafluoro-2-propylthio; and mercaptoalkylthio groups such as mercaptomethylthio, mercaptoethylthio, mercaptopropylthio, mercaptobutylthio, mercaptopentylthio, and mercaptooctylthio.

Examples of the unsubstituted C₁₋₂₀ alkylamino groups include methylamino, ethylamino, n-propylamino, iso-propylamino, n-butylamino, iso-butylamino, sec-butylamino, t-butylamino, n-pentylamino, iso-pentylamino, neo-pentylamino, 1,2-dimethylpropylamino, n-hexylamino, n-dodecylamino, 2-methylbutylamino, 2-methylpentylamino, cyclopentylamino, cyclohexylamino, 1,3-dimethylbutylamino, 1-iso-propylpropylamino, 1,2-dimethylbutylamino, n-heptylamino, 1,4-dimethylpentylamino, 2-methyl-1-iso-propylpropylamino, 1-ethyl-3-methylbutylamino, n-octylamino, 2-ethylhexylamino, 3-methyl-1-iso-propylbutylamino, 2,2-dimethyl-1-isopropyl-1-t-butylpropylamino and n-nonylamino groups. Exemplary substituted alkylamino groups include alkoxyalkylamino groups such as methoxymethylamino, methoxyethylamino, ethoxyethylamino, propoxyethylamino, butoxyethylamino, γ-methoxypropylamino, γ-ethoxypropylamino, methoxyethoxyethylamino, ethoxyethoxyethylamino, dimethoxymethylamino, diethoxymethylamino, dimethoxyethylamino, and diethoxyethylamino; halogenated alkylamino groups such as chloromethylamino, 2,2,2-trichloroethylamino, trifluoromethylamino, 1,1,1,3,3,3-hexafluoro-2-propylamino; and hydroxyalkylamino groups such as hydroxymethylamino, hydroxyethylamino, hydroxypropylamino, hydroxybutylamino, hydroxypentylamino, hydroxyoctylamino.

Illustrative of the unsubstituted C₂₋₂₀ dialkylamino group include dimethylamino, diethylamino, di(n-propyl)amino, di(iso-propyl)amino, di(n-butyl)amino, di(iso-butyl)amino, di(sec-butyl)amino, di(t-butyl)amino, di(n-pentyl)amino, di(iso-pentyl)amino, di(neo-pentyl)amino, di(1,2-dimethylpropyl)amino, di(n-hexyl)amino, di(n-dodecyl)amino, di(2-methylbutyl)amino, di(2-methylpentyl)amino, di(cyclopentyl)amino, di(cyclohexyl)amino, di(1,3-dimethylbutyl)amino, di(1-iso-propylpropyl)amino, di(1,2-dimethylbutyl)amino, di(n-heptyl)amino, di(1,4-dimethylpentyl)amino, di(2-methyl-1-iso-propylpropyl)amino, di(1-ethyl-3-methylbutyl)amino, di(n-octyl)amino, di(2-ethylhexyl)amino, di(3-methyl-1-iso-propylbutyl)amino, di(2,2,-dimethyl-1-iso-propyl-1-t-butylpropyl)amino and di(n-nonyl)amino groups. Examples of the substituted dialkylamino group include di(alkoxyalkyl)amino groups such as di(methoxymethyl)amino, di(methoxyethyl)amino, di(ethoxyethyl)amino, di(propoxyethyl)amino, di(butoxyethyl)amino, di(γ-methoxypropyl)amino, di(γ-ethoxypropyl)amino, di(methoxyethoxyethyl)amino, di(ethoxyethoxyethyl)amino, bis(dimethoxymethyl)amino, bis(diethoxymethyl)amino, bis(dimethoxyethyl)amino, bis(diethoxyethyl)amino; and di(halogenated alkyl)amino groups such as di(chloromethyl)amino, di(2,2,2-trichloroethyl)amino, di(trifluoromethyl)amino and di(1,1,1,3,3,3-hexafluoro-2-propyl)amino groups; and di(hydroxyalkyl)amino groups such as di(hydroxymethyl)amino, di(hydroxyethyl)amino, di(hydroxypropyl)amino, di(hydroxybutyl)amino, di(hydroxypentyl)amino, and di(hydroxyoctyl)amino.

Illustrative of the substituted or unsubstituted aryloxy group include a phenoxy group, which may be substituted by one or more alkyl groups such as methyl, ethyl, propyl, iso-propyl, butyl, 2-methylpropyl, pentyl and/or neo-pentyl, by one or more alkoxyl groups such as methoxy, ethoxy and/or propoxy, and/or by one or more halogen atoms such as chlorine, fluorine, bromine and/or iodine.

Illustrative of the substituted or unsubstituted arylthio group include a phenylthio group, which may be substituted by one or more alkyl groups such as methyl, ethyl, propyl, iso-propyl, butyl, 2-methylpropyl, pentyl and/or neo-pentyl, by one or more alkoxyl groups such as methoxy, ethoxy and/or propoxy, and/or by one or more halogen atoms such as chlorine, fluorine, bromine and/or iodine.

Examples of the halogen atom include chlorine, bromine, iodine and fluorine atoms.

Examples of the unsubstituted alkyl group represented by R¹⁷ include linear, branched and cyclic alkyl groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t-butyl, n-pentyl, iso-pentyl, neo-pentyl, 1,2-dimethylpropyl, n-hexyl, n-dodecyl, 2-methylbutyl, 2-methylpentyl, cyclopentyl, cyclohexyl, 1,3-dimethylbutyl, 1-iso-propylpropyl, 1,2-dimethylbutyl, n-heptyl, 1,4-dimethylpentyl, 2-methyl-1-iso-propylpropyl, 1-ethyl-3-methylbutyl, n-octyl, 2-ethylhexyl, 3-methyl-1-iso-propylbutyl, 2,2-dimethyl-1-iso-propyl-1-t-butylpropyl, and n-nonyl. Examples of the substituted alkyl group include alkoxyalkyl groups such as methoxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, γ-methoxypropyl, γ-ethoxypropyl, methoxyethoxyethyl, ethoxyethoxyethyl, dimethoxymethyl, diethoxymethyl, dimethoxyethyl, diethoxyethyl; halogenated alkyl groups such as chloromethyl, 2,2,2-trichloroethyl, trifluoromethyl, and 1,1,1,3,3,3-hexafluoro-2-propyl; and hydroxyalkyl groups such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyoctyl.

Examples of the metal represented by Met include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co and Fe and also include metal chlorides such as AlCl, InCl, FeCl, TiCl₂, SnCl₂, SiCl₂ and GeCl₂, metal oxides such as TiO and VO, and metal hydroxides such as Si(OH)₂.

Illustrative of the substituted or unsubstituted C₁₋₂₀ alkyl group represented by R¹⁸, R¹⁹ or R²⁰ in Formula (II) include those exemplified above with respect to the alkyl group in Formula (I). The connecting group represented by A can be any trivalent or tetravalent connecting group. Preferred examples of the trivalent connecting group include: ##STR8## One example of the tetravalent connecting group is ##STR9## The connecting group represented by B can be any divalent, trivalent or tetravalent connecting group. Preferred examples include --CH₂ --, --OCH₂ --, --OCH₂ CH₂ --, --OCH₂ CH₂ CH₂ --, --OCH₂ CH(CH₃)--, --OCH(CH₃)CH₂ --, --SCH₂ --, --SCH₂ CH₂ --, --SCH₂ CH₂ CH₂ --, --SCH₂ CH(CH₃)-- and --SCH(CH₃)CH₂ --. The connecting group represented by D can be any divalent, trivalent or tetravalent connecting group. Preferred examples include --CH₂ --, --OCH₂ --, --OCH₂ CH₂ --, --OCH₂ CH₂ CH₂ --, --OCH₂ CH(CH₃)--, --OCH(CH₃)CH₂ --, --SCH₂ --, --SCH₂ CH₂ --, --SCH₂ CH₂ CH₂ --, --SCH₂ CH(CH₃)--, --SCH(CH₃)CH₂ --, --CH(CH₃)--, --CH(CH₃)CH₂ --, --CH(CH₂ CH₃)-- and --CH(CH₂ CH₂ CH₃)--, with --CH₂ --, --OCH₂ --, --OCH₂ CH₂ --, --OCH₂ CH₂ CH₂ --, --OCH₂ CH(CH₃)-- and --OCH(CH₃)CH₂ -- being more preferred.

Specific phthalocyanine compounds include Compound Nos. I-1 to I-124 shown in Table 1. The phthalocyanine compounds may be mixtures of their available isomers. Especially, the phthalocyanine compounds ranging from Compound No. I-1 to Compound No. I-78 and from Compound No. I-121 to Compound No. 124 are suited for use in color filters, near infrared absorbers and optical recording media while the phthalocyanine compounds ranging from Compound No. I-79 to Compound No. I-120 are suited for use in color filters.

    TABLE 1                                                                           - Compound R.sup.1, R.sup.5, R.sup.9, R.sup.13 R.sup.2, R.sup.6,               R.sup.10, R.sup.14 R.sup.3, R.sup.7, R.sup.11, R.sup.15 R.sup.4,                R.sup.8, R.sup.12, R.sup.16 Met                                                  I-1                                                                             ##STR10##                                                                       H H H Cu                                                                       I-2                                                                              ##STR11##                                                                       H H H Cu                                                                       I-3                                                                              ##STR12##                                                                       H H H Cu                                                                       I-4                                                                              ##STR13##                                                                       H H H VO                                                                       I-5                                                                              ##STR14##                                                                       H H H Cu                                                                       I-6                                                                              ##STR15##                                                                       H H Cl Fe                                                                      I-7                                                                              ##STR16##                                                                       Br H Br Cu                                                                     I-8                                                                              ##STR17##                                                                       H H H Fe                                                                       I-9                                                                              ##STR18##                                                                       PhS PhS H Cu                                                                   I-10                                                                             ##STR19##                                                                       H H H Cu                                                                       I-11                                                                             ##STR20##                                                                       H H H Co                                                                       I-12                                                                             ##STR21##                                                                       H H H Cu                                                                       I-13                                                                             ##STR22##                                                                       H H H Cu                                                                       I-14                                                                             ##STR23##                                                                       H H H Zn                                                                       I-15                                                                             ##STR24##                                                                       Cl Cl                                                                           ##STR25##                                                                       Cu                                                                             I-16                                                                             ##STR26##                                                                       H H                                                                             ##STR27##                                                                       Fe                                                                             I-17                                                                             ##STR28##                                                                       Cl H                                                                            ##STR29##                                                                       Fe                                                                             I-18                                                                             ##STR30##                                                                       I I H VO                                                                       I-19                                                                             ##STR31##                                                                       I H Br VO                                                                      I-20                                                                             ##STR32##                                                                       Br Br H Cu                                                                     I-21                                                                             ##STR33##                                                                       Br Br Br Co                                                                    I-22                                                                             ##STR34##                                                                       H H H InCl                                                                     I-23                                                                             ##STR35##                                                                       SCH.sub.3 SCH.sub.3 H Cu                                                       I-24                                                                             ##STR36##                                                                       SPh SPh H Cu                                                                   I-25                                                                             ##STR37##                                                                       H H H Mn                                                                       I-26                                                                             ##STR38##                                                                       Br Br H Co                                                                     I-27                                                                             ##STR39##                                                                       Cl Cl Cl Fe                                                                    I-28                                                                             ##STR40##                                                                       H H H Zn                                                                       I-29                                                                             ##STR41##                                                                       ##STR42##                                                                       ##STR43##                                                                       ##STR44##                                                                       Cu                                                                             I-30                                                                             ##STR45##                                                                       H H                                                                             ##STR46##                                                                       Zn                                                                             I-31                                                                             ##STR47##                                                                       H Br H Cu                                                                      I-32                                                                             ##STR48##                                                                       H H Br Cu                                                                      I-33                                                                             ##STR49##                                                                       H I H Pd                                                                       I-34                                                                             ##STR50##                                                                       H H                                                                             ##STR51##                                                                       SiCl.sub.2                                                                     I-35                                                                             ##STR52##                                                                       SPh SPh                                                                         ##STR53##                                                                       Pb                                                                             I-36                                                                             ##STR54##                                                                       H H H Cu                                                                       I-37                                                                             ##STR55##                                                                       Br Br Br Cu                                                                    I-38                                                                             ##STR56##                                                                       H H                                                                             ##STR57##                                                                       VO                                                                             I-39                                                                             ##STR58##                                                                       Cl H H Fe                                                                      I-40                                                                             ##STR59##                                                                       H H                                                                             ##STR60##                                                                       Cu                                                                             I-41                                                                             ##STR61##                                                                       H H H Cu                                                                       I-42                                                                             ##STR62##                                                                       H H H Cu                                                                       I-43                                                                             ##STR63##                                                                       H H H Cu                                                                       I-44                                                                             ##STR64##                                                                       H H H Co                                                                       I-45                                                                             ##STR65##                                                                       H H H Cu                                                                       I-46                                                                             ##STR66##                                                                       H H H Fe                                                                       I-47                                                                             ##STR67##                                                                       H H H Fe                                                                       I-48                                                                             ##STR68##                                                                       H H H Cu                                                                       I-49                                                                             ##STR69##                                                                       H H H VO                                                                       I-50                                                                             ##STR70##                                                                       H H H InCl                                                                     I-51                                                                             ##STR71##                                                                       H H H SiCl.sub.2                                                               I-52                                                                             ##STR72##                                                                       H H H Zn                                                                       I-53                                                                             ##STR73##                                                                       H H Br InCl                                                                    I-54                                                                             ##STR74##                                                                       I H I Mn                                                                       I-55                                                                             ##STR75##                                                                       Cl Cl                                                                           ##STR76##                                                                       Cu                                                                             I-56                                                                             ##STR77##                                                                       H H Cl Cu                                                                      I-57                                                                             ##STR78##                                                                       H H H Cu                                                                       I-58                                                                             ##STR79##                                                                       SPh SPh H Cu                                                                   I-59                                                                             ##STR80##                                                                       SPh SPh Cl Pd                                                                  I-60                                                                             ##STR81##                                                                       H Br Br Co                                                                     I-61                                                                             ##STR82##                                                                       SCH.sub.3 SCH.sub.3 H Zn                                                       I-62                                                                             ##STR83##                                                                       H CH.sub.3 Br Fe                                                               I-63                                                                             ##STR84##                                                                       H C.sub.2                                                                       H.sub.5 H Fe                                                                            I-64                                                                    ##STR85##                                                                       NHC.sub.2 H.sub.5 NHC.sub.2                                                     H.sub.5 H VO                                                                                               I-65                                                 ##STR86##                                                                       OPh OPh H SiCl.sub.2                                                           I-66                                                                             ##STR87##                                                                       ##STR88##                                                                       ##STR89##                                                                       Cl Si(OH).sub.2                                                                I-67                                                                             ##STR90##                                                                       H H H Cu                                                                       I-68                                                                             ##STR91##                                                                       H H Cl VO                                                                      I-69                                                                             ##STR92##                                                                       ##STR93##                                                                       ##STR94##                                                                       H Cu                                                                           I-70                                                                             ##STR95##                                                                       COOCH.sub.3 H H Cu                                                             I-71                                                                             ##STR96##                                                                       N(CH.sub.3).sub.2 N(CH.sub.3).sub.2 H Co                                       I-72                                                                             ##STR97##                                                                       SH SH H Co                                                                     I-73                                                                             ##STR98##                                                                       H I I Mn                                                                       I-74                                                                             ##STR99##                                                                       ##STR100##                                                                      ##STR101##                                                                      H Fe                                                                           I-75                                                                             ##STR102##                                                                      H H                                                                             ##STR103##                                                                      Cu                                                                             I-76                                                                             ##STR104##                                                                      Cl H Cl Cu                                                                     I-77                                                                             ##STR105##                                                                      Cl H                                                                            ##STR106##                                                                      Cu                                                                             I-78                                                                             ##STR107##                                                                      I H                                                                             ##STR108##                                                                      Fe                                                                             I-79                                                                             ##STR109##                                                                      H H H Zn                                                                       I-80                                                                             ##STR110##                                                                      H H Br VO                                                                      I-81                                                                             ##STR111##                                                                      H H Cl VO                                                                      I-82                                                                             ##STR112##                                                                      H H CH.sub.3 VO                                                                I-83                                                                             ##STR113##                                                                      H Cl                                                                            ##STR114##                                                                      Pd                                                                             I-84                                                                             ##STR115##                                                                      H I                                                                             ##STR116##                                                                      Fe                                                                             I-85                                                                             ##STR117##                                                                      SPh SPh H Cu                                                                   I-86                                                                             ##STR118##                                                                      H H                                                                             ##STR119##                                                                      Cu                                                                             I-87                                                                             ##STR120##                                                                      Cl Cl Cl Cu                                                                    I-88                                                                             ##STR121##                                                                      H H                                                                             ##STR122##                                                                      Fe                                                                             I-89                                                                             ##STR123##                                                                      ##STR124##                                                                      ##STR125##                                                                      ##STR126##                                                                      Fe                                                                             I-90                                                                             ##STR127##                                                                      ##STR128##                                                                      ##STR129##                                                                      ##STR130##                                                                      Co                                                                             I-91                                                                             ##STR131##                                                                      H Cl Cl Pd                                                                     I-92                                                                             ##STR132##                                                                      H I I Ni                                                                       I-93                                                                             ##STR133##                                                                      NH(CH.sub.3) NH(CH.sub.3)                                                       ##STR134##                                                                      GeCl.sub.2                                                                     I-94                                                                             ##STR135##                                                                      H Cl                                                                            ##STR136##                                                                      Zn                                                                             I-95                                                                             ##STR137##                                                                      N(CH.sub.3).sub.2 N(CH.sub.3).sub.2 H Zn                                       I-96                                                                             ##STR138##                                                                      ##STR139##                                                                      ##STR140##                                                                      H Pb                                                                           I-97                                                                             ##STR141##                                                                      H H H Zn                                                                       I-98                                                                             ##STR142##                                                                      H H Br Cu                                                                      I-99                                                                             ##STR143##                                                                      H H Cl Ni                                                                       I-100                                                                          ##STR144##                                                                       H H                                                                             ##STR145##                                                                      Ni                                                                              I-101                                                                          ##STR146##                                                                       H Cl Cl Fe                                                                                                                                              V      -102                                                                             ##STR147##                                                                      COOC.sub.2                                                                      H.sub.5 H H Cu                                                                  I-103                                                                          ##STR148##                                                                       OH H Cl Zn                                                                      I-104                                                                          ##STR149##                                                                       H H H Pd                                                                        I-105                                                                          ##STR150##                                                                       H Cl Cl Pd                                                                      I-106                                                                          ##STR151##                                                                       H H                                                                             ##STR152##                                                                      Zn                                                                              I-107                                                                          ##STR153##                                                                       H H H SiCl.sub.2                                                                I-108                                                                          ##STR154##                                                                       H Br H Fe                                                                       I-109                                                                          ##STR155##                                                                       H H Br Co                                                                       I-110                                                                          ##STR156##                                                                       H H H Cu                                                                        I-111                                                                          ##STR157##                                                                       H H                                                                             ##STR158##                                                                      Pd                                                                              I-112                                                                          ##STR159##                                                                       H Cl Cl Pb                                                                      I-113                                                                          ##STR160##                                                                       H H H Cu                                                                        I-114                                                                          ##STR161##                                                                       H H                                                                             ##STR162##                                                                      Cu                                                                              I-115                                                                          ##STR163##                                                                       H Br Br Fe                                                                      I-116                                                                          ##STR164##                                                                       H H Br Fe                                                                       I-117                                                                          ##STR165##                                                                       H H H Fe                                                                        I-118                                                                          ##STR166##                                                                       H H Br Cu                                                                       I-119                                                                          ##STR167##                                                                       H H H Cu                                                                        I-120                                                                          ##STR168##                                                                       H H Cl Co                                                                       I-121                                                                          ##STR169##                                                                       OCH.sub.3 H H Cu                                                                I-122                                                                          ##STR170##                                                                       OCH.sub.3 OCH.sub.3 H Co                                                        I-123                                                                          ##STR171##                                                                       OCH.sub.3 H                                                                     ##STR172##                                                                      Cu                                                                              I-124                                                                          ##STR173##                                                                       H OC.sub.2                                                                      H.sub.5 H Pb                                                             

The dyes represented by the formula (I) can each be synthesized, for example, by reacting under heat a compound or a mixture of 2-4 compounds, all represented by the following formula (V) or (VI): ##STR174## wherein the benzene rings in the formulae (V) and (VI) may optionally have one or more substituents such as those described above in connection with the formula (I), with a metal compound, which is represented by the following formula (VII):

    Met-(Y).sub.d                                              (VII)

wherein Met is the same as Met in formula (I), Y means a monovalent or divalent ligand such as a halogen atom, an anionic acetate ion, acetylacetonato or oxygen atom, and d stands for an integer of 1-4, for example, in the presence of 1,8-diazabicyclo 5.4.0!-7-undecene (DBU), in a solvent such as an alcohol, an alkylaminourea, a halogenated hydrocarbon or quinoline, at 80°-230° C., for about 2-20 hours.

To fabricate a color filter for LCD or a color separation filter for image pickup tube by using one of the phthalocyanine compound of this invention, various processes can be used. For example, a photosensitive resin or photopolymerizable monomer is formed into a film on a substrate by casting, spin coating or the like. After the film being patterned by exposure to light, the resin layer is colored with the dye by dipping or the like. The filter is patterned by dry etching or lifting-off and then colored with the dye by vaccum deposition. The dye is either dissolved or dispersed beforehand in a photosensitive resin or photopolymerizable monomer. The solution or dispersion so prepared is formed into a film on a substrate by casting, spin coating or the like. The film is then patterned by exposure to light. As a still further alternative, such a solution or dispersion is applied in the form of a pattern by a printing method.

As has been described above, the patterning of a dye layer can be conducted on an optically transparent substrate. No particular limitation is imposed on the substrate to be used, insofar as it permits patterning of the dye layer and the color filter so formed functions as desired.

Examples of the substrate include glass plates; and films or plates of resins such as polyvinyl alcohol, hydroxyethylcellulose, methyl methacrylate, polyesters, polybutyral, polyamides, polyethylene, polyvinyl chloride, polyvinylidene chloride, polycarbonates, polyolefin copolymers, vinyl chloride copolymers, vinylidene chloride copolymers and styrene copolymers. A patterned dye layer can also be formed integrally with a substrate which is applied as a color filter. Examples of such a substrate includes the display screen of a cathode ray tube, the image receiving screen of an image pickup tube, a wafer with a solid-state image pickup device such as CCD, BBD, CID or BASIS formed thereon, a contact-type image sensor using a thin-film semiconductor, a liquid crystal display screen, and a photosensitive body or substrate for color electrophotography.

Taking the formation of a stripe filter as an example, a typical process for the formation of a filter will hereinafter be described with reference to the drawings.

First, one of the phthalocyanine compounds according to this invention is dissolved or dispersed at a proportion of 1-100 wt. %, preferably 40-100 wt. % in a photosensitive resin, and the resulting solution or dispersion is spin-coated on a substrate 1 by using a spinner (FIG. 1). The thickness of a resist layer 2 is usually 0.5-100 μm although it is determined depending on spectroscopic characteristics desired. After the resist layer 2 is dried, the resist layer 2 is pre-baked under suitable temperature conditions. The resist layer is exposed to light or an electron beam, to which the resist has sensitivity, via a mask 3 having a desired pattern corresponding to a pattern to be formed (i.e., a stripe pattern)--FIG. 2. The resist layer so exposed is then developed to form a pattern 4 (FIG. 3). If necessary, pre-treatment may be applied before the development to release any strain of the resist layer, or rinsing treatment may be conducted after the development to suppress any expansion of the resultant film. Finally, post-baking is applied under appropriate temperature conditions.

To form a color filter having two or more colors, the steps of from FIG. 1 to FIG. 3 are repeated using dyes corresponding to the respective colors as needed, namely, as many times as the number of filter colors employed, thereby making it possible to form, for example, a color filter having three colored layers 5,6,7 of different colors as shown in FIG. 4. To form a black matrix, the formation of colored layers may preferably be conducted after the formation of the black matrix.

To fabricate a color filter for a color copying machine or the like by using one of the phthalocyanine compound of this invention, various processes can be used. For example, it can be fabricated by mixing a thermoplastic resin, such as polystyrene, polymethyl methacrylate, polycarbonate, polyester or polyvinyl chloride, with 0.5-10 wt. %, based on the resin, of the dye of this invention and then injection-molding or drawing the resultant resin composition. It can also be fabricated by dissolving the dye of this invention either singly or together with a binder in a solvent and forming the resultant solution into a film on a substrate in accordance with casting, spin coating or the like. As a further alternative, the dye of this invention can be formed into a film on a substrate by vacuum evaporation. As a still further alternative, the dye of this invention is mixed with a varnish which contains a resin intermediate, and the resulting mixture is processed and then heat-treated into a resin.

As the material for the substrate in the above process, any resin can be used as long as it is optically transparent. Illustrative usable resins include acrylic resins, polyethylene, vinyl chloride resin, vinylidene chloride resin, polycarbonates, polyethylene copolymers, polyolefin copolymers, vinyl chloride copolymers, vinylidene chloride copolymers, and styrene copolymers.

To fabricate an optical recording medium by using one of the dyes according to the present invention, the dye can be coated or vacuum-evaporated on a transparent substrate. According to the coating process, a binder resin and the phthalocyanine compound are dissolved in a solvent such that the concentration of the binder resin is not higher than 20 wt. %, preferably 0 wt. % and that of the phthalocyanine compound is 0.05-20 wt. %, preferably 0.5-20 wt. %, and the resultant solution is coated by a spin coater. According to the vacuum evaporation process, the phthalocyanine compound is deposited on the substrate at 10⁻⁵ -10⁻⁷ torr and 100°-300° C.

To allow the phthalocyanine compound of this invention to exhibit good performance different from conventional dyes, spin-coating or dipping should be used. In particular, it is the best process to coat only the phthalocyanine compound of this invention. On the other hand, the optical recording medium can be either of the WORM type that only a recording layer comprising the phthalocyanine compound of this invention is provided on a substrate or of the CD-WORM type that the above recording layer is provided on a substrate, a reflective layer made of gold or aluminum is provided over the recording layer and an over-coat is applied further.

Any resin can be used for the production of the substrate as long as it is optically transparent. Illustrative usable resins include acrylic resins, polyethylene, vinyl chloride resin, vinylidene chloride resin, polycarbonate resins, polyethylene copolymers, polyolefin copolymers, vinyl chloride copolymers, vinylidene copolymers and styrene copolymers.

The substrate may have been surface-treated with a thermosetting resin or an ultraviolet curing resin.

To fabricate an optical recording medium (optical disc, optical card or the like), it is preferable from the standpoints of manufacturing cost and the handling ease by users to employ a polyacrylate substrate or polycarbonate substrate as a substrate and to coat and form a recording layer by spin coating.

In view of the solvent resistance of the substrate, illustrative solvents usable upon spin coating include halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, tetrachloroethylene and dichlorodifluoroethane; ethers such as tetrahydrofuran and diethyl ether; ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol and propanol; cellosolves such as methylcellosolve and ethylcellosolve; and hydrocarbons such as hexane, cyclohexane, octane, benzene, toluene and xylene.

The present invention will hereinafter be described in detail by the following examples. It should be borne in mind that embodiments of this invention should not be limited to or by the following examples.

EXAMPLE 1

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 10 g of 3-nitrophthalonitrile, 70 g of dried dimethylformamide (DMF) and 30 g of dried toluene were charged. They were thereafter converted completely into a solution, followed by cooling to 0° C. To the resulting solution, 100 g of a solution of 9.8 g of sodium oxide (the compound represented by the below-described formula VII-1), which had been prepared from sodium hydride, in DMF/toluene (7/3) was added dropwise at 0° to -5° C. After the temperature was raised to room temperature, the resulting solution was stirred for 2 hours. The target compound was obtained from the thus-obtained reaction mixture by extracting it with toluene and then purified by column chromatography, whereby 15 g of phthalonitrile (the compound represented by the below-described formula V-1) were obtained. ##STR175##

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 10 g (36.6 mmol) of the above-obtained phthalonitrile (V-1), 5.6 g of 1,8-diazabicyclo 5.4.0!-7-undecene and 100 g of n-amyl alcohol were charged, followed by heating to 110° C. in a nitrogen atmosphere. At the same temperature, 1.2 g (12 mmol) of CuCl were added, followed by reaction at 110°-120° C. for 8 hours. After the completion of the reaction, the reaction mixture was cooled and insoluble matter was removed by filtration. The filtrate was concentrated under reduced pressure to distill off the solvent. The residue was purified by column chromatography, whereby 8.2 g of a mixture consisting of the target compound (I-1) and its isomer(s) were obtained. Physical properties and elemental analysis data of the compound so obtained are shown below:

Visible absorption: λ_(max) =698 nm, εg=2.5×10⁵ ml/g·cm, (Solvent: toluene), Elemental analysis: C₆₀ H₇₆ N₁₂ O₈ Cu.

    ______________________________________                                                   C          H      N                                                  ______________________________________                                         Calculated (%)                                                                             62.31        6.58   14.54                                          Found (%)   62.30        6.60   14.52                                          ______________________________________                                    

In 10 g of a prepolymer ("SD-17", trade name; product of Dainippon Ink & Chemicals, Inc.), 5 g of the above-obtained phthalocyanine compound (I-1) and 5 g of "M/P Yellow 3GSL" (trade name; product of Mitsui Toatsu Dyes, Ltd.) were dissolved. A glass substrate was spin-coated with the resultant coating formulation by using a spinner. The substrate was prebaked at 85°-100° C. for 2-5 minutes and then exposed (20-30 mj/cm², 2 min.) to light from a high-pressure mercury lamp via a mask having a striped pattern. The resulting substrate was developed so that a pattern was formed thereon. Finally, the substrate was post-baked at 200°-230° C. for 10-30 minutes, whereby a filter with green stripes was obtained. The thickness of the dye layer was 2 μm.

The filter so obtained was superior in durability (moisture resistance, light resistance and heat resistance) and also in transmittance characteristics. The transmittance characteristics are shown in FIG. 5.

In addition, a solution (10 g/l) of the phthalocyanine compound (I-1) in n-octane was coated on a polycarbonate substrate, whereby an optical recording medium with gold as a reflective layer was fabricated. That optical recording medium showed 70% reflectance at 780-830 nm, and also 60 dB sensitivity as measured on the basis of reflection of a 780 nm laser beam of 7 mW from its substrate at 1800 rpm.

EXAMPLE 2

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 10 g of 3-nitrophthalonitrile, 70 g of dried dimethylformamide (DMF) and 30 g of dried toluene were charged. They were thereafter converted completely into a solution, followed by cooling to 0° C. To the resulting solution, 100 g of a solution of 11.4 g of sodium oxide (the compound represented by the below-described formula VII-2), which had been prepared from sodium hydride, in DMF/toluene (7/3) was added dropwise at 0° to -5° C. After the temperature was raised to room temperature, the resulting solution was stirred for 2 hours. The target compound was obtained from the thus-obtained reaction mixture by extracting it with toluene and then purified by column chromatography, whereby 16 g of phthalonitrile (the compound represented by the below-described formula V-2) were obtained. ##STR176##

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 15 g (49.8 mmol) of the above-obtained phthalonitrile (V-2), 7.6 g of 1,8-diazabicyclo 5.4.0!-7-undecene and 100 g of n-amyl alcohol were charged, followed by heating to 110° C. in a nitrogen atmosphere. At the same temperature, 1.48 g (14.9 mmol) of CuCl were added, followed by reaction at 110°-120° C. for 8 hours. After the completion of the reaction, the reaction mixture was cooled and insoluble matter was removed by filtration. The filtrate was concentrated under reduced pressure to distill off the solvent. The residue was purified by column chromatography, whereby 12 g of a mixture consisting of the target compound (I-2) and its isomer(s) were obtained. Physical properties and elemental analysis data of the compound so obtained are shown below:

Visible absorption: λ_(max) =698 nm, εg=2.4×10⁵ ml/g·cm, (Solvent: toluene), Elemental analysis: C₆₈ H₉₂ N₁₂ O₈ Cu.

    ______________________________________                                                   C          H      N                                                  ______________________________________                                         Calculated (%)                                                                             64.38        7.26   13.25                                          Found (%)   64.35        7.32   13.27                                          ______________________________________                                    

In a vessel equipped with a stirrer and a nitrogen inlet tube, 36.8 g of 4,4'-bis(2-aminophenoxy)biphenyl and 202 g of N,N-dimethylformamide were charged. 4,4'-(p-Phenylenedioxy)diphthalic dianhydride (39.8 g) were added in portions at room temperature in a nitrogen atmosphere, followed by stirring for 20 hours. To the resultant polyamidic acid solution, 3.0 g of the compound (I-2) and 3 g of "M/P Yellow 3GSL" were added and mixed. The mixture was thereafter cast on a glass substrate, followed by heat treatment at 200° C. for 5 hours. The filter so obtained was found to have not only good transmittance characteristics but also excellent durability. Its transmittance characteristics are shown in FIG. 6.

In addition, a solution of the phthalocyanine compound (I-2) in n-octane (10 g/l) was coated on a polycarbonate substrate, whereby an optical recording medium with gold as a reflective layer was fabricated. That optical recording medium showed 72% reflectance at 780-830 nm, and also 61 dB sensitivity as measured on the basis of reflection of a 780 nm laser beam of 7 mW from its substrate at 1800 rpm.

EXAMPLE 3

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 10 g of 3-nitrophthalonitrile, 70 g of dried dimethylformamide (DMF) and 30 g of dried toluene were charged. They were thereafter converted completely into a solution, followed by cooling to 0° C. To the resulting solution, 100 g of a solution of 13.8 g of sodium oxide (the compound represented by the below-described formula VII-3), which had been prepared from sodium hydride, in DMF/toluene (7/3) was added dropwise at 0° to -5° C. After the temperature was raised to room temperature, the resulting solution was stirred for 2 hours. The target compound was obtained from the thus-obtained reaction mixture by extracting it with toluene and then purified by column chromatography, whereby 16 g of phthalonitrile (the compound represented by the below-described formula V-3) were obtained. ##STR177##

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 15 g (43.7 mmol) of the above-obtained phthalonitrile (V-3), 6.65 g of 1,8-diazabicyclo 5.4.0!-7-undecene and 130 g of n-amyl alcohol were charged, followed by heating to 110° C. in a nitrogen atmosphere. At the same temperature, 1.3 g (13.1 mmol) of CuCl were added, followed by reaction at 110°-120° C. for 8 hours. After the completion of the reaction, the reaction mixture was cooled and insoluble matter was removed by filtration. The filtrate was concentrated under reduced pressure to distill off the solvent. The residue was purified by column chromatography, whereby 12.5 g of a mixture consisting of the target compound (I-3) and its isomer(s) were obtained. Physical properties and elemental analysis data of the compound so obtained are shown below:

Visible absorption: λ_(max) =698 nm, εg=2.6×10⁵ ml/g·cm, (Solvent: toluene), Elemental analysis: C₈₀ H₁₁₆ N₁₂ O₈ Cu.

    ______________________________________                                                   C          H      N                                                  ______________________________________                                         Calculated (%)                                                                             66.88        8.08   11.70                                          Found (%)   66.82        8.13   11.71                                          ______________________________________                                    

One gram of the phthalocyanine compound (I-3) and 1 g of "M/P Yellow YL" (trade name; product of Mitsui Toatsu Dyes, Ltd.) were added to 100 g of polystyrene. The resulting resin composition was injection-molded, whereby a filter was fabricated. The filter so obtained was found to have not only good transmittance characteristics but also excellent durability. Its transmittance characteristics are shown in FIG. 7.

In addition, a solution (10 g/l) of the phthalocyanine compound (I-3) in n-octane was coated on a polycarbonate substrate, whereby an optical recording medium with gold as a reflective layer was fabricated. That optical recording medium showed 73% reflectance at 780-830 nm, and 62 dB sensitivity as measured on the basis of reflection of a 780 nm laser beam of 7 mW from its substrate at 1800 rpm.

COMPARATIVE EXAMPLE 1

Using a known dye, a filter was fabricated in a similar manner to Example 1. Characteristics of the filter so obtained are shown in Table 2. In addition, transmittance characteristics of the filter are shown in FIG. 8.

COMPARATIVE EXAMPLE 2

A filter was fabricated by coloring gelatin with a known dye. Characteristics of the filter so obtained are shown in Table 2. In addition, transmittance characteristics of the filter are shown in FIG. 9.

                  TABLE 2                                                          ______________________________________                                                Transmittance                                                                           Moisture   Light   Heat                                               character-                                                                              resist-    resist- resist-                                            istics   ance       ance    ance                                        ______________________________________                                         Example 1                                                                               A (FIG. 5) A          A     A                                         Example 2                                                                               A (FIG. 6) A          A     A                                         Comp. Ex. 1.sup.1)                                                                      C (FIG. 8) A          B     A                                         Comp. Ex. 2.sup.2)                                                                      A (FIG. 9) C          C     C                                         ______________________________________                                    

1) Employed was the dye disclosed in Japanese Patent Laid-Open No. 233401/1989 and having the following structural formula. ##STR178## 2) Employed was "Acid Green 16", a dye described on page 48 of "Development Market Trend of Special Function Dyes in 1990's" published by CMC Press, Inc.

The following methods and standards were followed for the measurements of the respective characteristics and for the evaluation of the measurement results.

1. Transmittance characteristics

A: Maximum transmittance ≧80%, with the proviso that the transmittance is 10% or lower at (the wavelength for the maximum transmittance ±50) nm.

C: Maximum transmittance ≧70%, with the proviso that the transmittance is 10% or lower at (the wavelength for the maximum transmittance ±50) nm.

2. Moisture resistance

Color difference was determined after each filter was stored at 95% R.H. and 60° C. for 200 hours.

A: ΔE≦3

C: ΔE≧5

3. Light resistance

Color difference was determined after each filter was exposed to light from a fadeometer at 60° C. for 200 hours.

A: ΔE≦3

B: 3<ΔE<5

C: ΔE≧5

4. Heat resistance

Color difference was determined after each filter was stored at 250° C. for 1 hour.

A: ΔE≦3

C: ΔE≧5

COMPARATIVE TESTS

Table 3 shows the maximum absorption wavelength (λ_(max)) of the compound obtained in each example and the molecular absorption coefficient (ε) of the compound at the maximum wavelength, both as measured in the form of a solution, and the solubility, maximum reflectance and sensitivity of the compound, in comparison with those of the known compounds to be described next.

COMPARATIVE EXAMPLE 3

Compound No. 4 exemplified in Japanese Patent Laid-Open No. 152769/1986 ##STR179##

The above compound was dissolved in chloroform because of its insolubility in n-hexane. The resulting solution was coated on a polycarbonate substrate. The substrate so coated was evaluated as a medium.

COMPARATIVE EXAMPLE 4

Compound described in Example 1 of Japanese Patent Laid-Open No. 209583/1985 ##STR180##

The above compound was dissolved in chloroform because of its insolubility in n-hexane. The resulting solution was coated on a polycarbonate substrate. The substrate so coated was evaluated as a medium.

COMPARATIVE EXAMPLE 5

Compound No. 10 exemplified in Japanese Patent Laid-Open No. 197280/1986

    Deca(--OC.sub.5 H.sub.11)--H.sub.2 Pc

A solution of the above compound in carbon tetrachloride was coated on a polycarbonate plate. The substrate so coated was evaluated as a medium.

                  TABLE 3                                                          ______________________________________                                                                   Maximum                                                               Solu-    reflec-  Sensi-                                              λ.sub.max (ε)                                                            bility   tance (%)                                                                               tivity                                      ______________________________________                                         Example 1 698 (2.5 × 10.sup.5)                                                                A        42     A                                         Example 2 698 (2.4 × 10.sup.5)                                                                A        30     A                                         Comp. Ex. 3                                                                              740 (1.5 × 10.sup.5)                                                                C        24     B                                         Comp. Ex. 4                                                                              780 (1.5 × 10.sup.5)                                                                C        27     B                                         Comp. Ex. 5                                                                              760 (1.5 × 10.sup.5)                                                                B        20     C                                         ______________________________________                                    

The following methods and standards were followed for the measurements of the respective characteristics and for the evaluation of the measurement results.

1. Maximum absorption wavelength (λ_(max)) and molecular absorption coefficient (ε) at the wavelength

Measured at a concentration of 5 mg/l in toluene or chloroform.

2. Solubility

A: Solubility of 5 g/l or more in n-hexane.

B: Solubility of less than 5 g/l in n-hexane but 5 g/l or more in carbon tetrachloride.

C: Solubility of less than 5 g/l in carbon tetrachloride.

3. Maximum reflectance (%)

The maximum reflectance is the reflectance obtained when a 5 g/l solution in n-hexane is coated on a polycarbonate substrate by a spin-coater and the substrate so obtained is then exposed to light of 780 nm.

4. Sensitivity

The sensitivity is expressed in terms of a C/N ratio as measured upon writing at a linear velocity of 5.5 m/sec with a 780 nm semiconductor laser beam of 8 mW.

A: C/N≧40 (dB)

B: 40>C/N≧30 (dB)

C: C/N<30 (dB)

EXAMPLE 4

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 10 g of 3-nitrophthalonitrile, 70 g of dried dimethylformamide (DMF) and 30 g of dried toluene were charged. They were thereafter converted completely into a solution, followed by cooling to 0° C. To the resulting solution, 100 g of a solution of 15.4 g of sodium oxide (the compound represented by the below-described formula VII-4), which had been prepared from sodium hydride, in DMF/toluene (7/3) was added dropwise at 0° to -5° C. After the temperature was raised to room temperature, the resulting solution was stirred for 2 hours. The target compound was obtained from the thus-obtained reaction mixture by extracting it with toluene and then purified by column chromatography, whereby 17 g of phthalonitrile (the compound represented by the below-described formula V-4) were obtained. ##STR181##

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 15 g (40.4 mmol) of the above-obtained phthalonitrile (V-4), 6.2 g of 1,8-diazabicyclo 5.4.0!-7-undecene and 100 g of n-amyl alcohol were charged, followed by heating to 110° C. in a nitrogen atmosphere. At the same temperature, 3.2 g (12.1 mmol) of VO(acac)₂ were added, followed by reaction at 110°-120° C. for 8 hours. After the completion of the reaction, the reaction mixture was cooled and insoluble matter was removed by filtration. The filtrate was concentrated under reduced pressure to distill off the solvent. The residue was purified by column chromatography, whereby 13 g of a mixture consisting of the target compound (I-4) and its isomer(s) were obtained. Physical properties and elemental analysis data of the compound so obtained are shown below:

Visible absorption: λ_(max) =725 nm, εg=2.3×10⁵ ml/g·cm, (Solvent: toluene), Elemental analysis: C₈₈ H₁₃₂ N₁₂ O₉ V.

    ______________________________________                                                   C          H      N                                                  ______________________________________                                         Calculated (%)                                                                             68.09        8.51   10.83                                          Found (%)   68.08        8.53   10.82                                          ______________________________________                                    

One gram of the phthalocyanine compound (I-4) was added to 100 g of polystyrene. The resulting resin composition was injection-molded, whereby a filter was fabricated. The filter so obtained was found to have not only good transmittance characteristics but also excellent durability.

In addition, a solution (10 g/l) of the phthalocyanine compound (I-4) in n-octane was coated on a polycarbonate substrate, whereby an optical recording medium with gold as a reflective layer was fabricated. That optical recording medium showed 71% reflectance at 780-830 nm, and 64 dB sensitivity as measured on the basis of reflection of a 780 nm laser beam of 7 mW from its substrate at 1800 rpm.

EXAMPLE 5

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 10 g of 3-nitrophthalonitrile, 70 g of dried dimethylformamide (DMF) and 30 g of dried toluene were charged. They were thereafter converted completely into a solution, followed by cooling to 0° C. To the resulting solution, 100 g of a solution of 18.6 g of sodium oxide (the compound represented by the below-described formula VII-5), which had been prepared from sodium hydride, in DMF/toluene (7/3) was added dropwise at 0° to -5° C. After the temperature was raised to room temperature, the resulting solution was stirred for 2 hours. The target compound was obtained from the thus-obtained reaction mixture by extracting it with toluene and then purified by column chromatography, whereby 18 g of phthalonitrile (the compound represented by the below-described formula V-5) were obtained. ##STR182##

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 15 g (35.1 mmol) of the above-obtained phthalonitrile (V-5), 5.34 g of 1,8-diazabicyclo 5.4.0!-7-undecene and 120 g of n-amyl alcohol were charged, followed by heating to 110° C. in a nitrogen atmosphere. At the same temperature, 1.04 g (10.5 mmol) of CuCl were added, followed by reaction at 110°-120° C. for 8 hours. After the completion of the reaction, the reaction mixture was cooled and insoluble matter was removed by filtration. The filtrate was concentrated under reduced pressure to distill off the solvent. The residue was purified by column chromatography, whereby 13 g of a mixture consisting of the target compound (I-5) and its isomer(s) were obtained. Physical properties and elemental analysis data of the compound so obtained are shown below:

Visible absorption: λ_(max) =700 nm, εg=2.6×10⁵ ml/g·cm, (Solvent: toluene), Elemental analysis: C₁₀₄ H₁₆₄ N₁₂ O₈ Cu.

    ______________________________________                                                   C          H      N                                                  ______________________________________                                         Calculated (%)                                                                             70.45        9.26   9.48                                           Found (%)   70.30        9.32   9.45                                           ______________________________________                                    

Mixed into a homogeneous solution were 122 g of 1,4-bis(α,α-dimethylisocyanatomethyl)benzene, 117 g of 1,3,5-tris(3-mercaptopropyl)isocyanurate, 10 g of the compound (I-5) and 0.3 g of dibutyltin dilaurate. The solution was poured into a mold formed of glasses, which had been subjected to surface treatment with a fluorine-base external mold releasing agent, with PVC gasket.

After heated at 70° C. for 4 hours, at 80° C. for 2 hours, at 90° C. for 2 hours, at 100° C. for 2 hours and at 120° C. for 2 hours, the mold was cooled and the filter so molded was released. The filter exhibited good transmittance characteristics and were also excellent in light resistance and moisture resistance.

In addition, a solution (10 g/l) of the phthalocyanine compound (I-5) in n-octane was coated on a polycarbonate substrate, whereby an optical recording medium with gold as a reflective layer was fabricated. That optical recording medium showed 73% reflectance at 780-830 nm, and 61 dB sensitivity as measured on the basis of reflection of a 780 nm laser beam of 7 mW from its substrate at 1800 rpm.

EXAMPLE 6

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 10 g of 6-chloro-3-nitrophthalonitrile, 70 g of dried dimethylformamide (DMF) and 30 g of dried toluene were charged. They were thereafter converted completely into a solution, followed by cooling to 0° C. To the resulting solution, 100 g of a solution of 10.2 g of sodium oxide (the compound represented by the below-described formula VII-6), which had been prepared from sodium hydride, in DMF/toluene (7/3) was added dropwise at 0° to -5° C. After the temperature was raised to room temperature, the resulting solution was stirred for 2 hours. The target compound was obtained from the thus-obtained reaction mixture by extracting it with toluene and then purified by column chromatography, whereby 13 g of phthalonitrile (the compound represented by the below-described formula V-6) were obtained. ##STR183##

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 10 g (28.6 mmol) of the above-obtained phthalonitrile (V-6), 4.3 g of 1,8-diazabicyclo 5.4.0!-7-undecene and 100 g of n-amyl alcohol were charged, followed by heating to 110° C. in a nitrogen atmosphere. At the same temperature, 1.08 g (8.5 mmol) of FeCl₂ were added, followed by reaction at 110°-120° C. for 8 hours. After the completion of the reaction, the reaction mixture was cooled and insoluble matter was removed by filtration. The filtrate was concentrated under reduced pressure to distill off the solvent. The residue was purified by column chromatography, whereby 8.1 g of a mixture consisting of the target compound (I-6) and its isomer(s) were obtained. Physical properties and elemental analysis data of the compound so obtained are shown below:

Visible absorption: λ_(max) =707 nm, εg=2.3×10⁵ ml/g·cm, (Solvent: toluene), Elemental analysis: C₇₂ H₉₆ N₁₂ O₈ Cl₄ Fe.

    ______________________________________                                                   C          H      N                                                  ______________________________________                                         Calculated (%)                                                                             59.43        6.60   11.56                                          Found (%)   59.42        6.62   11.57                                          ______________________________________                                    

A solution (10 g/l) of the phthalocyanine compound (I-6) in n-octane was coated on a polycarbonate substrate, whereby an optical recording medium with gold as a reflective layer was fabricated. That optical recording medium showed 72% reflectance at 780-830 nm, and 65 dB sensitivity as measured on the basis of reflection of a 780 nm laser beam of 7 mW from its substrate at 1800 rpm.

In addition, 100 g of polymethyl methacrylate and 3 g of the compound (I-6) were dissolved in 500 g of chloroform. The resulting solution was cast on a glass substrate and was then dried. The filter so fabricated was found to have good durability and filtering characteristics.

EXAMPLE 7

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 10 g of 4,6-dibromo-3-nitrophthalonitrile, 70 g of dried dimethylformamide (DMF) and 30 g of dried toluene were charged. They were thereafter converted completely into a solution, followed by cooling to 0° C. To the resulting solution, 100 g of a solution of 7.3 g of sodium oxide (the compound represented by the below-described formula VII-7), which had been prepared from sodium hydride, in DMF/toluene (7/3) was added dropwise at 0° to -5° C. After the temperature was raised to room temperature, the resulting solution was stirred for 2 hours. The target compound was obtained from the thus-obtained reaction mixture by extracting it with toluene and then purified by column chromatography, whereby 13 g of phthalonitrile (the compound represented by the below-described formula V-7) were obtained. ##STR184##

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 12 g (23.9 mmol) of the above-obtained phthalonitrile (V-7), 3.6 g of 1,8-diazabicyclo 5.4.0!-7-undecene and 100 g of n-amyl alcohol were charged, followed by heating to 110° C. in a nitrogen atmosphere. At the same temperature, 0.71 g (7.2 mmol) of CuCl was added, followed by reaction at 110°-120° C. for 8 hours. After the completion of the reaction, the reaction mixture was cooled and insoluble matter was removed by filtration. The filtrate was concentrated under reduced pressure to distill off the solvent. The residue was purified by column chromatography, whereby 11 g of a mixture consisting of the target compound (I-7) and its isomer(s) were obtained. Physical properties and elemental analysis data of the compound so obtained are shown below:

Visible absorption: λ_(max) =710 nm, εg=2.5×10⁵ ml/g·cm, (Solvent: toluene), Elemental analysis: C₇₆ H₁₀₀ N₁₂ O₁₂ Br₈ Cu.

    ______________________________________                                                   C          H      N                                                  ______________________________________                                         Calculated (%)                                                                             43.96        4.82   8.10                                           Found (%)   43.98        4.85   8.11                                           ______________________________________                                    

One gram of the phthalocyanine compound (I-7) was added to 100 g of polystyrene. The resulting resin composition was injection-molded, whereby a filter was fabricated. The filter so obtained was found to have not only good transmittance characteristics but also have excellent durability.

In addition, a solution (10 g/l) of the phthalocyanine compound (I-7) in n-octane was coated on a polycarbonate substrate, whereby an optical recording medium with gold as a reflective layer was fabricated. That optical recording medium showed 72% reflectance at 780-830 nm, and 63 dB sensitivity as measured on the basis of reflection of a 780 nm laser beam of 7 mW from its substrate at 1800 rpm.

EXAMPLE 8

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 10 g of 3-nitrophthalonitrile, 70 g of dried dimethylformamide (DMF) and 30 g of dried toluene were charged. They were thereafter converted completely into a solution, followed by cooling to 0° C. To the resulting solution, 100 g of a solution of 15.6 g of sodium oxide (the compound represented by the below-described formula VII-8), which had been prepared from sodium hydride, in DMF/toluene (7/3) was added dropwise at 0° to -5° C. After the temperature was raised to room temperature, the resulting solution was stirred for 2 hours. The target compound was obtained from the thus-obtained reaction mixture by extracting it with toluene and then purified by column chromatography, whereby 18 g of phthalonitrile (the compound represented by the below-described formula V-8) were obtained. ##STR185##

In a vessel equipped with a stirrer, a reflux condenser and an ammonia gas inlet tube, 15 g of the above-obtained phthalonitrile (V-8), 100 g of methanol and 1.1 g of sodium methylate were charged, followed by the blowing of ammonia gas at a molar ratio of 6.4 times relative to the compound V-8. After the contents were heated to 55°-60° C., they were reacted under heating for 2 hours. Methanol was thereafter distilled off under reduced pressure and organic substance was extracted with toluene. Hexane was added to precipitate crystals, whereby 14 g of the target compound (VI-1) were obtained. ##STR186##

A mixture consisting of 2.3 g of FeCl₂ and 100 g of quinoline was heated to 200° C. To the mixture, 10 g of the above-obtained diiminoisoindoline derivative (VI-1) were added, followed by heating under reflux for 5 hours. The reaction mixture was poured into 500 g of methanol. After suction filtration, crystals so collected were washed with methanol, followed by drying, whereby 8.2 g of a mixture consisting of the compound (I-8) and its isomer(s) were obtained. Physical properties and elemental analysis data of the compound so obtained are shown below.

Visible absorption: λ_(max) =708 nm, εg=2.6×10⁵ ml/g·cm, (Solvent: toluene), Elemental analysis: C₈₄ H₁₂₄ N₁₂ O₁₂ Fe.

    ______________________________________                                                   C          H      N                                                  ______________________________________                                         Calculated (%)                                                                             65.12        8.01   10.85                                          Found (%)   65.10        8.03   10.90                                          ______________________________________                                    

In 100 g of dibutyl ether, 1 g of the phthalocyanine compound (I-8) was dissolved. The resulting solution was coated on a polycarbonate substrate for optical disc. The optical disc thus fabricated was found to have a reflectance of 36% and a sensitivity of 51 dB in terms of C/N ratio as measured at a linear velocity of 5.5 m/sec by a 780 nm laser beam of 8 mW.

In addition, a solution of 1 g of the phthalocyanine compound (I-8) in 100 g of dibutyl ether was coated on the polycarbonate substrate for optical card and the surface of the recording layer was coated with a resin, whereby an optical card was fabricated. That optical card was found to have a reflectance of 36% and a sensitivity of 53 dB in terms of C/N ratio as measured at a linear velocity of 2.8 m/sec by a 780 nm laser beam of 8 mW.

EXAMPLE 9

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 10 g of 4,5-diphenylthio-3-nitrophthalonitrile, 70 g of dried dimethylformamide (DMF) and 30 g of dried toluene were charged. They were thereafter converted completely into a solution, followed by cooling to 0° C. To the resulting solution, 100 g a solution of 7.6 g of sodium oxide (the compound represented by the below-described formula VII-9), which had been prepared from sodium hydride, in of DMF/toluene (7/3) was added dropwise at 0° to -5° C. After the temperature was raised to room temperature, the resulting solution was stirred for 2 hours. The target compound was obtained from the thus-obtained reaction mixture by extracting it with toluene and then purified by column chromatography, whereby 15 g of phthalonitrile (the compound represented by the below-described formula V-9) were obtained. ##STR187##

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 15 g (24.3 mmol) of the above-obtained phthalonitrile (V-9), 3.7 g of 1,8-diazabicyclo 5.4.0!-7-undecene and 100 g of chloronaphthalene were charged, followed by heating to 110° C. in a nitrogen atmosphere. At the same temperature, 0.72 g (7.3 mmol) of CuCl was added, followed by reaction at 110°-120° C. for 8 hours. After the completion of the reaction, the reaction mixture was cooled and insoluble matter was removed by filtration. The filtrate was concentrated under reduced pressure to distill off the solvent. The residue was purified by column chromatography, whereby 11 g of a mixture consisting of the target compound (I-9) and its isomer(s) were obtained. Physical properties and elemental analysis data of the compound so obtained are shown below:

Visible absorption: λ_(max) =745 nm, εg=2.6×10⁵ ml/g·cm, (Solvent: toluene), Elemental analysis: C₁₄₀ H₁₇₂ N₁₂ O₁₂ S₈ Cu.

    ______________________________________                                                   C          H      N                                                  ______________________________________                                         Calculated (%)                                                                             66.36        6.79   6.64                                           Found (%)   66.32        6.80   6.67                                           ______________________________________                                    

In 10 g of a photoresist ("TPR", trade name; product of Tokyo Ohka Kogyo Co., Ltd.), 5 g of the above-obtained phthalocyanine compound (I-9) and 5 g of "M/P Yellow F3G" (trade name; product of Mitsui Toatsu Dyes, Ltd.) were dissolved. A glass substrate was spin-coated with the resultant coating formulation by using a spinner. The substrate was prebaked at 85°-100° C. for 2-5 minutes and then exposed (20-30 mj/cm², 2 min.) to light from a high-pressure mercury lamp via a mask having a striped pattern. The resulting substrate was developed so that a pattern was formed thereon. Finally, the substrate was post-baked at 200°-230° C. for 10-30 minutes, whereby a filter with green stripes was obtained. The thickness of the dye layer was 2 μm.

The filter so obtained was superior in durability (moisture resistance, light resistance and heat resistance) and also in transmittance characteristics.

In addition, a solution (10 g/l) of the phthalocyanine compound (I-9) in n-octane was coated on a polycarbonate substrate, whereby an optical recording medium with gold as a reflective layer was fabricated. That optical recording medium showed 70% reflectance at 780-830 nm, and 60 dB sensitivity as measured on the basis of reflection of a 780 nm laser beam of 7 mW from its substrate at 1800 rpm.

EXAMPLES 10-50

In each example, one to four of the phthalonitriles represented by the below-described formula (V) (Table 4) or of the diiminoisoindolines represented by the below-described formula (VI) (Table 5) were reacted with a metal derivative under the conditions shown in Table 6, whereby a phthalocyanine compound and its isomer(s) were both synthesized. A filter fabricated using the thus-obtained compound was found to be excellent in both transmittance characteristics and durability. In addition, an optical recording medium fabricated using the compound was found to have good reflectance, sensitivity and durability. ##STR188##

    TABLE 4                                                                           - Intermediate R.sup.1 R.sup.2 R.sup.3 R.sup.4                                  V-10                                                                            H H H                                                                          V-11                                                                             ##STR189##                                                                      H H H                                                                          V-12                                                                             ##STR190##                                                                      H H H                                                                          V-13                                                                             ##STR191##                                                                      H H H                                                                          V-14                                                                             ##STR192##                                                                      H H H                                                                          V-15                                                                             ##STR193##                                                                      Cl Cl                                                                           ##STR194##                                                                     V-16                                                                             ##STR195##                                                                      H H                                                                             ##STR196##                                                                     V-17                                                                             ##STR197##                                                                      Cl H                                                                            ##STR198##                                                                     V-18                                                                             ##STR199##                                                                      I I H                                                                          V-19                                                                             ##STR200##                                                                      I H Br                                                                         V-20                                                                             ##STR201##                                                                      Br Br H                                                                        V-21                                                                             ##STR202##                                                                      Br Br Br                                                                       V-22                                                                             ##STR203##                                                                      H H H                                                                          V-23                                                                             ##STR204##                                                                      SCH.sub.3 SCH.sub.3 H                                                          V-24                                                                             ##STR205##                                                                      SPh SPh H                                                                      V-25                                                                             ##STR206##                                                                      H H H                                                                          V-26                                                                             ##STR207##                                                                      Br Br H                                                                        V-27                                                                             ##STR208##                                                                      Cl Cl Cl                                                                       V-28                                                                             ##STR209##                                                                      H H H                                                                          V-29                                                                             ##STR210##                                                                      ##STR211##                                                                      ##STR212##                                                                      ##STR213##                                                                     V-30                                                                             ##STR214##                                                                      H H                                                                             ##STR215##                                                                     V-31                                                                             ##STR216##                                                                      H Br H                                                                         V-32                                                                             ##STR217##                                                                      H H Br                                                                         V-33                                                                             ##STR218##                                                                      H I H                                                                          V-34                                                                             ##STR219##                                                                      H H                                                                             ##STR220##                                                                     V-35                                                                             ##STR221##                                                                      SPh SPh                                                                         ##STR222##                                                                     V-36                                                                             ##STR223##                                                                      H H H                                                                          V-37                                                                             ##STR224##                                                                      Br Br Br                                                                       V-38                                                                             ##STR225##                                                                      H H                                                                             ##STR226##                                                                     V-39                                                                             ##STR227##                                                                      Cl H H                                                                         V-40                                                                             ##STR228##                                                                      H H                                                                             ##STR229##                                                               

                  TABLE 5                                                          ______________________________________                                         Inter-                                                                         mediate                                                                               R.sup.1                 R.sup.2                                                                              R.sup.3                                                                            R.sup.4                               ______________________________________                                         VI-2                                                                                   ##STR230##             H     H   H                                     VI-3                                                                                   ##STR231##             H     H   H                                     VI-4                                                                                   ##STR232##             H     H   H                                     VI-5                                                                                   ##STR233##             H     H   H                                     VI-6                                                                                   ##STR234##             H     H   H                                     VI-7                                                                                   ##STR235##             H     H   H                                     VI-8                                                                                   ##STR236##             H     H   H                                     VI-9                                                                                   ##STR237##             H     H   H                                     VI-10                                                                                  ##STR238##             H     H   H                                     VI-11                                                                                  ##STR239##             H     H   H                                     ______________________________________                                    

                  TABLE 6                                                          ______________________________________                                         Cmp'd     Metal    Preparation process                                                                             λ.sub.max                           ______________________________________                                         I-10      Cu       Reaction of CuCl, the                                                                           699                                                           intermediate (V-10) and                                                        DBU in amyl alcohol                                         I-11      Co       Reaction of CoCl.sub.21 the                                                                     693                                                           intermediate (V-11) and                                                        DBU in amyl alcohol                                         I-12      Cu       Reaction of CuCl, the                                                                           700                                                           intermediate (V-12) and                                                        DBU in amyl alcohol                                         I-13      Cu       Reaction of CuCl, the                                                                           699                                                           intermediate (V-13) and                                                        DBU in amyl alcohol                                         I-14      Zn       Reaction of Zn(OAc).sub.2, the                                                                  702                                                           intermediate (V-14) and                                                        DBU in amyl alcohol                                         I-15      Cu       Reaction of CuCl, the                                                                           770                                                           intermediate (V-15) and                                                        DBU in amyl alcohol                                         I-16      Fe       Reaction of FeCl.sub.2, the                                                                     758                                                           intermediate (V-16) and                                                        DBU in amyl alcohol                                         I-17      Fe       Reaction of FeCl.sub.2, the                                                                     765                                                           intermediate (V-17) and                                                        DBU in amyl alcohol                                         I-18      VO       Reaction of VO(acac).sub.2, the                                                                 720                                                           intermediate (V-18) and                                                        DBU in amyl alcohol                                         I-19      VO       Reaction of VO(acac).sub.2, the                                                                 725                                                           intermediate (V-19) and                                                        DBU in amyl alcohol                                         I-20      Cu       Reaction of CuCl, the                                                                           705                                                           intermediate (V-20) and                                                        DBU in amyl alcohol                                         I-21      Co       Reaction of CoCl.sub.2, the                                                                     710                                                           intermediate (V-21) and                                                        DBU in amyl alcohol                                         I-22      InCl     Reaction of InCl.sub.3, the                                                                     720                                                           intermediate (V-22) and                                                        DBU in amyl alcohol                                         I-23      Cu       Reaction of CuCl, the                                                                           745                                                           intermediate (V-23) and                                                        DBU in amyl alcohol                                         I-24      Cu       Reaction of CuCl, the                                                                           750                                                           intermediate (V-24) and                                                        DBU in amyl alcohol                                         I-25      Mn       Reaction of MnCl.sub.2, the                                                                     685                                                           intermediate (V-25) and                                                        DBU in amyl alcohol                                         I-26      Co       Reaction of CoCl.sub.2, the                                                                     715                                                           intermediate (V-26) and                                                        DBU in chloronaphthalene                                    I-27      Fe       Reaction of FeCl.sub.2, the                                                                     705                                                           intermediate (V-27) and                                                        DBU in chloronaphthalene                                    I-28      Zn       Reaction of Zn(OAc).sub.2, the                                                                  710                                                           intermediate (V-28) and                                                        DBU in chloronaphthalene                                    I-29      Cu       Reaction of CuCl, the                                                                           790                                                           intermediate (V-29) and                                                        DBU in chloronaphthalene                                    I-30      Zn       Reaction of Zn(OAc).sub.2, the                                                                  745                                                           intermediate (V-30) and                                                        DBU in chloronaphthalene                                    I-31      Cu       Reaction of CuCl, the                                                                           705                                                           intermediate (V-31) and                                                        DBU in chloronaphthalene                                    I-32      Cu       Reaction of CuCl, the                                                                           706                                                           intermediate (V-32) and                                                        DBU in chloronaphthalene                                    I-33      Pd       Reaction of PdCl.sub.2, the                                                                     695                                                           intermediate (V-33) and                                                        DBU in chloronaphthalene                                    I-34      SiCl.sub.2                                                                              Reaction of SiCl.sub.4, the                                                                     750                                                           intermediate (V-34) and                                                        DBU in amyl alcohol                                         I-35      Pb       Reaction of Pb(OAc).sub.2, the                                                                  797                                                           intermediate (V-35) and                                                        DBU in amyl alcohol                                         I-36      Cu       Reaction of CuCl, the                                                                           760                                                           intermediate (V-36) and                                                        DBU in amyl alcohol                                         I-37      Cu       Reaction of CuCl, the                                                                           720                                                           intermediate (V-37) and                                                        DBU in amyl alcohol                                         I-38      VO       Reaction of VO(acac).sub.2, the                                                                 775                                                           intermediate (V-38) and                                                        DBU in amyl alcohol                                         I-39      Fe       Reaction of FeCl.sub.2, the                                                                     685                                                           intermediate (V-39) and                                                        DBU in chloronaphthalene                                    I-40      Cu       Reaction of CuCl, the                                                                           687                                                           intermediate (V-40) and                                                        DBU in amyl alcohol                                         I-41      Cu       Reaction of CuCl and the                                                                        702                                                           intermediate (VI-2) in                                                         quinoline                                                   I-42      Cu       Reaction of CuCl and the                                                                        703                                                           intermediate (VI-3) in                                                         quinoline                                                   I-43      Cu       Reaction of CuCl and the                                                                        702                                                           intermediate (VI-4) in                                                         quinoline                                                   I-44      Co       Reaction of CoCl.sub.2 and the                                                                  700                                                           intermediate (VI-5) in                                                         quinoline                                                   I-45      Cu       Reaction of CuCl and the                                                                        703                                                           intermediate (VI-6) in                                                         quinoline                                                   I-46      Fe       Reaction of FeCl.sub.2 and the                                                                  710                                                           intermediate (VI-7) in                                                         quinoline                                                   I-47      Fe       Reaction of FeCl.sub.2 and the                                                                  711                                                           intermediate (VI-8) in                                                         quinoline                                                   I-48      Cu       Reaction of CuCl and the                                                                        703                                                           intermediate (VI-9) in                                                         quinoline                                                   I-49      VO       Reaction of VO(acac).sub.2 and                                                                  720                                                           the intermediate (VI-10)                                                       in quinoline                                                I-50      InCl     Reaction of InCl.sub.3 and the                                                                  715                                                           intermediate (VI-11) in                                                        quinoline                                                   ______________________________________                                          ##STR240##                                                               

EXAMPLE 51

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 10 g of 3-nitrophthalonitrile, 70 g of dried dimethylformamide (DMF) and 30 g of dried toluene were charged. They were thereafter converted completely into a solution, followed by cooling to 0° C. To the resulting solution, 100 g of a solution of 22.5 g of sodium sulfide (the compound represented by the below-described formula VII-10), which had been prepared from sodium hydride, in DMF/toluene (7/3) was added dropwise at 0° to -5° C. After the temperature was raised to room temperature, the resulting solution was stirred for 2 hours. The target compound was obtained from the thus-obtained reaction mixture by extracting it with toluene and then purified by column chromatography, whereby 19 g of phthalonitrile (the compound represented by the below-described formula V-41) were obtained. ##STR241##

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 15.5 g (31.3 mmol) of the above-obtained phthalonitrile (V-41), 4.8 g of 1,8-diazabicyclo 5.4.0!-7-undecene and 100 g of n-amyl alcohol were charged, followed by heating to 110° C. in a nitrogen atmosphere. At the same temperature, 1.6 g (9.4 mmol) of SiCl₄ were added, followed by reaction at 110°-120° C. for 8 hours. After the completion of the reaction, the reaction mixture was cooled and insoluble matter was removed by filtration. The filtrate was concentrated under reduced pressure to distill off the solvent. The residue was purified by column chromatography, whereby 10.5 g of a mixture consisting of the target compound (I-51) and its isomer(s) were obtained. Physical properties and elemental analysis data of the compound so obtained are shown below:

Visible absorption: λ_(max) =710 nm, εg=2.3×10⁵ ml/g·cm, (Solvent: toluene), Elemental analysis: C₉₆ H₁₄₈ N₁₂ S₁₆ Cl₂ Si.

    ______________________________________                                                   C          H      N                                                  ______________________________________                                         Calculated (%)                                                                             55.41        7.12   8.08                                           Found (%)   55.40        7.15   8.09                                           ______________________________________                                    

In 10 g of a prepolymer ("SD-17", trade name; product of Dainippon Ink & Chemicals, Inc.), 1 g of the above-obtained phthalocyanine compound (I-51) and 1 g of "M/P Yellow 3GSL" (trade name; product of Mitsui Toatsu Dyes, Ltd.) were dissolved. A glass substrate was spin-coated with the resultant coating formulation by using a spinner. After being dried, the substrate was prebaked at 85°-100° C. for 2-5 minutes and then exposed (20-30 mj/cm², 2 min.) to light from a high-pressure mercury lamp via a mask having a striped pattern. The resulting substrate was developed so that a pattern was formed thereon. Finally, the substrate was post-baked at 200°-230° C. for 10-30 minutes, whereby a filter with green stripes was obtained. The thickness of the dye layer was 1 μm.

The filter so obtained was superior in durability (moisture resistance, light resistance and heat resistance) and also in transmittance characteristics.

In addition, a solution (10 g/l) of the phthalocyanine compound (I-51) in n-octane was coated on a polycarbonate substrate, whereby an optical recording medium with gold as a reflective layer was fabricated. That optical recording medium showed 73% reflectance at 780-830 nm, and 58 dB sensitivity as measured on the basis of reflection of a 780 nm laser beam of 7 mW from its substrate at 1800 rpm.

EXAMPLE 52

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 10 g of 3-nitrophthalonitrile, 70 g of dried dimethylformamide (DMF) and 30 g of dried toluene were charged. They were thereafter converted completely into a solution, followed by cooling to 0° C. To the resulting solution, 100 g of a solution of 20.9 g of sodium sulfide (the compound represented by the below-described formula VII-11), which had been prepared from sodium hydride, in DMF/toluene (7/3) was added dropwise at 0° to -5° C. After the temperature was raised to room temperature, the resulting solution was stirred for 2 hours. The target compound was obtained from the thus-obtained reaction mixture by extracting it with toluene and then purified by column chromatography, whereby 18.5 g of phthalonitrile (the compound represented by the below-described formula V-42) were obtained. ##STR242##

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 15 g (32.3 mmol) of the above-obtained phthalonitrile (V-42), 4.9 g of 1,8-diazabicyclo 5.4.0!-7-undecene and 110 g of n-amyl alcohol were charged, followed by heating to 110° C. in a nitrogen atmosphere. At the same temperature, 1.78 g (9.7 mmol) of Zn(OAc)₂ were added, followed by reaction at 110°-120° C. for 8 hours. After the completion of the reaction, the reaction mixture was cooled and insoluble matter was removed by filtration. The filtrate was concentrated under reduced pressure to distill off the solvent. The residue was purified by chromatography, whereby 13 g of a mixture consisting of the target compound (I-52) and its isomer(s) were obtained. Physical properties and elemental analysis data of the compound so obtained are shown below:

Visible absorption: λ_(max) =705 nm, εg=2.5×10⁵ ml/g·cm, (Solvent: toluene), Elemental analysis: C₈₈ H₁₃₂ N₁₂ S₁₆ Zn.

    ______________________________________                                                   C          H      N                                                  ______________________________________                                         Calculated (%)                                                                             54.62        6.83   8.69                                           Found (%)   54.60        6.85   8.70                                           ______________________________________                                    

In a vessel equipped with a stirrer and a nitrogen inlet tube, 36.8 g of 4,4'-bis(2-aminophenoxy)biphenyl and 202 g of N,N-dimethylformamide were charged. 4,4'-(p-Phenylenedioxy)diphthalic dianhydride (39.8 g) were added in portions at room temperature in a nitrogen atmosphere, followed by stirring for 20 hours. To the resultant polyamidic acid solution, 3.0 g of the compound (I-52) were added and mixed. The mixture was thereafter cast on a glass substrate, followed by heat treatment at 200° C. for 5 hours. The filter so obtained was found to have not only good transmittance characteristics but also excellent durability.

In addition, a solution of the phthalocyanine compound (I-52) in n-octane (10 g/l) was coated on a polycarbonate substrate, whereby an optical recording medium with gold as a reflective layer was fabricated. That optical recording medium showed 70% reflectance at 780-830 nm, and 59 dB sensitivity as measured on the basis of reflection of a 780 nm laser beam of 7 mW from its substrate at 1800 rpm.

EXAMPLE 53

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 10 g of 6-bromo-3-nitrophthalonitrile, 70 g of dried dimethylformamide (DMF) and 30 g of dried toluene were charged. They were thereafter converted completely into a solution, followed by cooling to 0° C. To the resulting solution, 100 g of a solution of 16.4 g of sodium sulfide (the compound represented by the below-described formula VII-12), which had been prepared from sodium hydride, in DMF/toluene (7/3) was added dropwise at 0° to -5° C. After the temperature was raised to room temperature, the resulting solution was stirred for 2 hours. The target compound was obtained from the thus-obtained reaction mixture by extracting it with toluene and then purified by column chromatography, whereby 13 g of phthalonitrile (the compound represented by the below-described formula V-43) were obtained. ##STR243##

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 10 g (16.6 mmol) of the above-obtained phthalonitrile (V-43), 2.5 g of 1,8-diazabicyclo 5.4.0!-7-undecene and 120 g of n-amyl alcohol were charged, followed by heating to 110° C. in a nitrogen atmosphere. At the same temperature, 1.35 g (6.1 mmol) of InCl₃ were added, followed by reaction at 110°-120° C. for 8 hours. After the completion of the reaction, the reaction mixture was cooled and insoluble matter was removed by filtration. The filtrate was concentrated under reduced pressure to distill off the solvent. The residue was purified by column chromatography, whereby 8.1 g of a mixture consisting of the target compound (I-53) and its isomer(s) were obtained. Physical properties and elemental analysis data of the compound so obtained are shown below:

Visible absorption: λ_(max) =715 nm, εg=2.2×10⁵ ml/g·cm, (Solvent: toluene), Elemental analysis: C₁₀₄ H₁₆₀ N₁₂ S₁₆ ClBr4In

    ______________________________________                                                   C          H      N                                                  ______________________________________                                         Calculated (%)                                                                             48.79        6.26   6.57                                           Found (%)   48.81        6.30   6.60                                           ______________________________________                                    

One gram of the phthalocyanine compound (I-53) was added to 100 g of polystyrene. The resulting resin composition was injection-molded, whereby a filter was fabricated. The filter so obtained was found to have not only good transmittance characteristics but also have excellent durability.

In addition, a solution (10 g/l) of the phthalocyanine compound (I-53) in n-octane was coated on a polycarbonate substrate, whereby an optical recording medium with gold as a reflective layer was fabricated. That optical recording medium showed 73% reflectance at 780-830 nm, and 60 dB sensitivity as measured on the basis of reflection of a 780 nm laser beam of 7 mW from its substrate at 1800 rpm.

EXAMPLE 54

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 10 g of 4,6-diiodo-3-nitrophthalonitrile, 70 g of dried dimethylformamide (DMF) and 30 g of dried toluene were charged. They were thereafter converted completely into a solution, followed by cooling to 0° C. To the resulting solution, 100 g of a solution of 9.5 g of sodium sulfide (the compound represented by the below-described formula VII-13), which had been prepared from sodium hydride, in DMF/toluene (7/3) was added dropwise at 0° to -5° C. After the temperature was raised to room temperature, the resulting solution was stirred for 2 hours. The target compound was obtained from the thus-obtained reaction mixture by extracting it with toluene and then purified by column chromatography, whereby 13 g of phthalonitrile (the compound represented by the below-described formula V-44) were obtained. ##STR244##

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 12 g (16.4 mmol) of the above-obtained phthalonitrile (V-44), 2.5 g of 1,8-diazabicyclo 5.4.0!-7-undecene and 120 g of n-amyl alcohol were charged, followed by heating to 110° C. in a nitrogen atmosphere. At the same temperature, 0.6 g (4.7 mmol) of MnCl₂ was added, followed by reaction at 110°-120° C. for 8 hours. After the completion of the reaction, the reaction mixture was cooled and insoluble matter was removed by filtration. The filtrate was concentrated under reduced pressure to distill off the solvent. The residue was purified by column chromatography, whereby 10.1 g of a mixture consisting of the target compound (I-54) and its isomer(s) were obtained. Physical properties and elemental analysis data of the compound so obtained are shown below:

Visible absorption: λ_(max) =716 nm, εg=2.3×10⁵ ml/g·cm, (Solvent: toluene), Elemental analysis: C₁₀₀ H₁₄₈ N₁₂ S₁₆ I₈ Mn.

    ______________________________________                                                   C          H      N                                                  ______________________________________                                         Calculated (%)                                                                             38.73        4.78   5.42                                           Found (%)   38.72        4.79   5.43                                           ______________________________________                                    

One gram of the phthalocyanine compound (I-54) was added to 100 g of polystyrene. The resulting resin composition was injection-molded, whereby a filter was fabricated. The filter so obtained was found to have not only good transmittance characteristics but also have excellent durability.

In addition, a solution (10 g/l) of the phthalocyanine compound (I-54) in n-octane was coated on a polycarbonate substrate, whereby an optical recording medium with gold as a reflective layer was fabricated. That optical recording medium showed 72% reflectance at 780-830 nm, and 61 dB sensitivity as measured on the basis of reflection of a 780 nm laser beam of 7 mW from its substrate at 1800 rpm.

EXAMPLE 55

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 10 g of 4,5-dichloro-3,6-di-nitrophthalonitrile, 70 g of dried dimethylformamide (DMF) and 30 g of dried toluene were charged. They were thereafter converted completely into a solution, followed by cooling to 0° C. To the resulting solution, 100 g of a solution of 20.3 g of sodium sulfide (the compound represented by the below-described formula VII-14), which had been prepared from sodium hydride, in DMF/toluene (7/3) was added dropwise at 0° to -5° C. After the temperature was raised to room temperature, the resulting solution was stirred for 2 hours. The target compound was obtained from the thus-obtained reaction mixture by extracting it with toluene and then purified by column chromatography, whereby 24 g of phthalonitrile (the compound represented by the below-described formula V-45) were obtained. ##STR245##

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 20 g (26.8 mmol) of the above-obtained phthalonitrile (V-45), 4.1 g of 1,8-diazabicyclo 5.4.0!-7-undecene and 100 g of n-amyl alcohol were charged, followed by heating to 110° C. in a nitrogen atmosphere. At the same temperature, 1.15 g (11.6 mmol) of CuCl were added, followed by reaction at 110°-120° C. for 8 hours. After the completion of the reaction, the reaction mixture was cooled and insoluble matter was removed by filtration. The filtrate was concentrated under reduced pressure to distill off the solvent. The residue was purified by column chromatography, whereby 13 g of a mixture consisting of the target compound (I-55) and its isomer(s) were obtained. Physical properties and elemental analysis data of the compound so obtained are shown below:

Visible absorption: λ_(max) =775 nm, εg=2.5×10⁵ ml/g·cm, (Solvent: toluene), Elemental analysis: C₁₄₄ H₂₄₀ N₁₂ S₁₆ Cl₈ Cu.

    ______________________________________                                                   C          H      N                                                  ______________________________________                                         Calculated (%)                                                                             56.63        7.87   7.34                                           Found (%)   56.62        7.89   7.34                                           ______________________________________                                    

Mixed into a homogeneous solution were 122 g of 1,4-bis(α,α-dimethylisocyanatomethyl)benzene, 117 g of 1,3,5-tris(3-mercaptopropyl)isocyanurate, 10 g of the compound (I-55) and 0.3 g of dibutyltin dilaurate. The solution was poured into a mold formed of glasses, which had been subjected to surface treatment with a fluorine-base external mold releasing agent, with PVC gasket.

After heated at 70° C. for 4 hours, at 80° C. for 2 hours, at 90° C. for 2 hours, at 100° C. for 2 hours and at 120° C. for 2 hours, the mold was cooled and the filter so molded was released. The filter exhibited good transmittance characteristics and were also excellent in light resistance and moisture resistance.

In addition, a solution (10 g/l) of the phthalocyanine compound (I-55) in n-octane was coated on a polycarbonate substrate, whereby an optical recording medium with gold as a reflective layer was fabricated. That optical recording medium showed 69% reflectance at 780-830 nm, and 62 dB sensitivity as measured on the basis of reflection of a 780 nm laser beam of 7 mW from its substrate at 1800 rpm.

EXAMPLE 56

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 10 g of 6-chloro-3-nitrophthalonitrile, 70 g of dried dimethylformamide (DMF) and 30 g of dried toluene were charged. They were thereafter converted completely into a solution, followed by cooling to 0° C. To the resulting solution, 100 g of a solution of 18.6 g of sodium sulfide (the compound represented by the below-described formula VII-15), which had been prepared from sodium hydride, in DMF/toluene (7/3) was added dropwise at 0° to -5° C. After the temperature was raised to room temperature, the resulting solution was stirred for 2 hours. The target compound was obtained from the thus-obtained reaction mixture by extracting it with toluene and then purified by column chromatography, whereby 19 g of phthalonitrile (the compound represented by the below-described formula V-46) were obtained. ##STR246##

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 15 g (28.6 mmol) of the above-obtained phthalonitrile (V-46), 4.3 g of 1,8-diazabicyclo 5.4.0!-7-undecene and 110 g of n-amyl alcohol were charged, followed by heating to 110° C. in a nitrogen atmosphere. At the same temperature, 0.85 g (8.6 mmol) of CuCl was added, followed by reaction at 110°-120° C. for 8 hours. After the completion of the reaction, the reaction mixture was cooled and insoluble matter was removed by filtration. The filtrate was concentrated under reduced pressure to distill off the solvent. The residue was purified by column chromatography, whereby 10.5 g of a mixture consisting of the target compound (I-56) and its isomer(s) were obtained. Physical properties and elemental analysis data of the compound so obtained are shown below:

Visible absorption: λ_(max) =712 nm, εg=2.2×10⁵ ml/g·cm, (Solvent: toluene), Elemental analysis: C₁₀₄ H₁₆₀ N₁₂ S₁₂ Cl₄ Cu.

    ______________________________________                                                   C          H      N                                                  ______________________________________                                         Calculated (%)                                                                             57.63        7.39   7.76                                           Found (%)   57.62        7.40   7.77                                           ______________________________________                                    

One gram of the phthalocyanine compound (I-56) was added to 100 g of polystyrene. The resulting resin composition was injection-molded, whereby a filter was fabricated. The filter so obtained was found to have not only good transmittance characteristics but also excellent durability.

A solution (10 g/l) of the phthalocyanine compound (I-56) in n-octane was coated on a polycarbonate substrate, whereby an optical recording medium with gold as a reflective layer was fabricated. That optical recording medium showed 70% reflectance at 780-830 nm, and 60 dB sensitivity as measured on the basis of reflection of a 780 nm laser beam of 7 mW from its substrate at 1800 rpm.

EXAMPLE 57

In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 10 g of 3-nitrophthalonitrile, 70 g of dried dimethylformamide (DMF) and 30 g of dried toluene were charged. They were thereafter converted completely into a solution, followed by cooling to 0° C. To the resulting solution, 100 g of a solution of 23.5 g of sodium sulfide (the compound represented by the below-described formula VII-16), which had been prepared from sodium hydride, in DMF/toluene (7/3) was added dropwise at 0° to -5° C. After the temperature was raised to room temperature, the resulting solution was stirred for 2 hours. The target compound was obtained from the thus-obtained reaction mixture by extracting it with toluene and then purified by column chromatography, whereby 21 g of phthalonitrile (the compound represented by the below-described formula V-47) were obtained. ##STR247##

In a vessel equipped with a stirrer, a reflux condenser and an ammonia gas inlet tube, 20 g of the above-obtained phthalonitrile (V-47), 200 g of methanol and 1.1 g of sodium methylate were charged, followed by the blowing of ammonia gas at a molar ratio of 6.4 times relative to the compound V-47. After the contents were heated to 55°-60° C., they were reacted under heating for 2 hours. Methanol was thereafter distilled off under reduced pressure and organic substance was extracted with toluene. Hexane was added and crystals were precipitated, whereby 18 g of the target compound (VI-12) were obtained. ##STR248##

A mixture consisting of 1.01 g of CuCl and 300 g of quinoline was heated to 200° C. To the mixture, 18 g of the above-obtained diiminoisoindoline derivative (VI-12) were added, followed by heating under reflux for 5 hours. The reaction mixture was poured into 1000 g of methanol. After suction filtration, crystals so collected were washed with methanol, followed by drying, whereby 16 g of a mixture consisting of the compound (I-57) and its isomer(s) were obtained. Physical properties and elemental analysis data of the compound so obtained are shown below.

Visible absorption: λ_(max) =709 nm, εg=2.4×10⁵ ml/g·cm, (Solvent: toluene), Elemental analysis: C₁₀₀ H₁₅₆ N₁₂ S₁₆ Cu.

    ______________________________________                                                   C          H      N                                                  ______________________________________                                         Calculated (%)                                                                             57.16        7.43   8.00                                           Found (%)   57.14        7.53   8.03                                           ______________________________________                                    

One gram of the phthalocyanine compound (I-57) was added to 100 g of polystyrene. The resulting resin composition was injection-molded, whereby a filter was fabricated. The filter so obtained was found to have not only good transmittance characteristics but also excellent durability.

One gram of the phthalocyanine compound (I-57) was dissolved in 100 g of dibutyl ether and the resulting solution was coated on a polycarbonate substrate for optical disc. The optical disc thus fabricated was found to have a reflectance of 36% and a sensitivity of 51 dB in terms of C/N ratio as measured at a linear velocity of 5.5 m/sec by a 780 nm laser beam of 8 mW.

A solution (10 g/l) of the phthalocyanine compound (I-57) in n-octane was coated on a polycarbonate substrate, whereby an optical recording medium with gold as a reflective layer was fabricated. That optical recording medium showed 70% reflectance at 780-830 nm, and 57 dB sensitivity as measured on the basis of reflection of a 780 nm laser beam of 7 mW from its substrate at 1800 rpm.

EXAMPLES 58-124

In each example, one to four of the phthalonitriles represented by the below-described formula (V) (Table 7) or of the diiminoisoindolines represented by the below-described formula (VI) (Table 8) were reacted with a metal derivative under the conditions shown in Table 9, whereby a phthalocyanine compound and its isomer(s) were both synthesized. A filter fabricated using the thus-obtained compound was found to be excellent in transmittance characteristics and durability. In addition, an optical recording medium fabricated using the respective compound of from I-58 to I-78 was found to have good reflectance, sensitivity and durability. ##STR249##

    TABLE 7                                                                           - Intermediate R.sup.1 R.sup.2 R.sup.3 R.sup.4                                  V-48                                                                            ##STR250##                                                                      ##STR251##                                                                      H                                                                              V-49                                                                             ##STR252##                                                                      COOCH.sub.3 H H                                                                V-50                                                                             ##STR253##                                                                      N(CH.sub.3).sub.2 N(CH.sub.3).sub.2 H                                          V-51                                                                             ##STR254##                                                                      SH SH H                                                                        V-52                                                                             ##STR255##                                                                      H I I                                                                          V-53                                                                             ##STR256##                                                                      ##STR257##                                                                      ##STR258##                                                                      H                                                                              V-54                                                                             ##STR259##                                                                      H H                                                                             ##STR260##                                                                     V-55                                                                             ##STR261##                                                                      Cl H Cl                                                                        V-56                                                                             ##STR262##                                                                      Cl H                                                                            ##STR263##                                                                     V-57                                                                             ##STR264##                                                                      I H                                                                             ##STR265##                                                                     V-58                                                                             ##STR266##                                                                      H H H                                                                          V-59                                                                             ##STR267##                                                                      H H Br                                                                         V-60                                                                             ##STR268##                                                                      H H Cl                                                                         V-61                                                                             ##STR269##                                                                      H H CH.sub.3                                                                   V-62                                                                             ##STR270##                                                                      H Cl                                                                            ##STR271##                                                                     V-63                                                                             ##STR272##                                                                      H I                                                                             ##STR273##                                                                     V-64                                                                             ##STR274##                                                                      SPh SPh H                                                                      V-65                                                                             ##STR275##                                                                      H H                                                                             ##STR276##                                                                     V-66                                                                             ##STR277##                                                                      Cl Cl Cl                                                                       V-67                                                                             ##STR278##                                                                      H H                                                                             ##STR279##                                                                     V-68                                                                             ##STR280##                                                                      ##STR281##                                                                      ##STR282##                                                                      ##STR283##                                                                     V-69                                                                             ##STR284##                                                                      ##STR285##                                                                      ##STR286##                                                                      ##STR287##                                                                     V-70                                                                             ##STR288##                                                                      H Cl Cl                                                                        V-71                                                                             ##STR289##                                                                      H I I                                                                          V-72                                                                             ##STR290##                                                                      NH(CH.sub.3) NH(CH.sub.3)                                                       ##STR291##                                                                     V-73                                                                             ##STR292##                                                                      H Cl                                                                            ##STR293##                                                                     V-74                                                                             ##STR294##                                                                      N(CH.sub.3).sub.2 N(CH.sub.3).sub.2  H                                         V-75                                                                             ##STR295##                                                                      ##STR296##                                                                      ##STR297##                                                                      H                                                                              V-76                                                                             ##STR298##                                                                      H H H                                                                          V-77                                                                             ##STR299##                                                                      H H Br                                                                         V-78                                                                             ##STR300##                                                                      H H Cl                                                                         V-79                                                                             ##STR301##                                                                      H H                                                                             ##STR302##                                                                     V-80                                                                             ##STR303##                                                                      H Cl Cl                                                                        V-81                                                                             ##STR304##                                                                      COOC.sub.2                                                                      H.sub.5 H H                                                                               V-82                                                                  ##STR305##                                                                      OH H CL                                                                        V-83                                                                             ##STR306##                                                                      H H H                                                                          V-84                                                                             ##STR307##                                                                      H Cl Cl                                                                        V-85                                                                             ##STR308##                                                                      H H                                                                             ##STR309##                                                                     V-86                                                                             ##STR310##                                                                      H H H                                                                          V-87                                                                             ##STR311##                                                                      H Br H                                                                         V-88                                                                             ##STR312##                                                                      H H Br                                                                         V-89                                                                             ##STR313##                                                                      H H H                                                                          V-90                                                                             ##STR314##                                                                      H H                                                                             ##STR315##                                                                     V-91                                                                             ##STR316##                                                                      H Cl Cl                                                                        V-92                                                                             ##STR317##                                                                      H H H                                                                          V-93                                                                             ##STR318##                                                                      H H                                                                             ##STR319##                                                                     V-94                                                                             ##STR320##                                                                      H Br Br                                                                        V-95                                                                             ##STR321##                                                                      H H Br                                                                         V-96                                                                             ##STR322##                                                                      H H H                                                                          V-97                                                                             ##STR323##                                                                      H H Br                                                                         V-98                                                                             ##STR324##                                                                      H H H                                                                          V-99                                                                             ##STR325##                                                                      H H Cl                                                                         V-100                                                                            ##STR326##                                                                      OCH.sub.3 H H                                                                  V-101                                                                            ##STR327##                                                                      OCH.sub.3 OCH.sub.3 H                                                          V-102                                                                            ##STR328##                                                                      OCH.sub.3 H                                                                     ##STR329##                                                                     V-103                                                                            ##STR330##                                                                      H OC.sub.2                                                                      H.sub.5 H                                                                

                                      TABLE 8                                      __________________________________________________________________________     Intermediate                                                                         R.sup.1                   R.sup.2    R.sup.3    R.sup.4                  __________________________________________________________________________     VI-13                                                                                 ##STR331##               SPh        SPh        H                        VI-14                                                                                 ##STR332##               SPh        SPh        Cl                       VI-15                                                                                 ##STR333##               H          Br         Br                       VI-16                                                                                 ##STR334##               SCH.sub.3  SCH.sub.3  H                        VI-17                                                                                 ##STR335##               H          CH.sub.3   Br                       VI-18                                                                                 ##STR336##               H          C.sub.2 H.sub.5                                                                           H                        VI-19                                                                                 ##STR337##               NHC.sub.2 H.sub.5                                                                         NHC.sub.2 H.sub.5                                                                         H                        VI-20                                                                                 ##STR338##               OPh        OPh        H                        VI-21                                                                                 ##STR339##                                                                                               ##STR340##                                                                                ##STR341##                                                                               Cl                       VI-22                                                                                 ##STR342##               H          H          H                        VI-23                                                                                 ##STR343##               H          H          Cl                       __________________________________________________________________________

                  TABLE 9                                                          ______________________________________                                         Cmp'd    Metal     Preparation process                                                                            λ.sub.max                            ______________________________________                                         I-58     Cu        Reaction of CuCl and the                                                                       761                                                            intermediate (VI-13) in                                                        quinoline                                                   I-59     Pd        Reaction of PdCl.sub.2 and the                                                                 758                                                            intermediate (VI-14) in                                                        quinoline                                                   I-60     Co        Reaction of CoCl.sub.2 and the                                                                 710                                                            intermediate (VI-15) in                                                        quinoline                                                   I-61     Zn        Reaction of Zn(OAc).sub.2 and                                                                  735                                                            the intermediate (V-16)                                                        in quinoline                                                I-62     Fe        Reaction of FeCl.sub.2 and the                                                                 708                                                            intermediate (VI-17) in                                                        quinoline                                                   I-63     Fe        Reaction of FeCl.sub.2 and the                                                                 705                                                            intermediate (VI-18) in                                                        quinoline                                                   I-64     VO        Reaction of VO(acac).sub.2 and                                                                 740                                                            the intermediate (V-19)                                                        in quinoline                                                I-65     SiCl.sub.2                                                                               Reaction of SiCl.sub.4 and the                                                                 725                                                            intermediate (VI-20) in                                                        quinoline                                                   I-66     Si(OH).sub.2                                                                             Hydrolysis with ammonia                                                                        719                                                            after reaction of SiCl.sub.4 and                                               the intermediate (VI-21) in                                                    quinoline                                                   I-67     Cu        Reaction of CuCl and the                                                                       705                                                            intermediate (VI-22) in                                                        quinoline                                                   I-68     VO        Reaction of VO(acac).sub.2 and                                                                 725                                                            the intermediate (VI-23)                                                       in quinoline                                                I-69     Cu        Reaction of CuCl, the                                                                          760                                                            intermediate (V-48) and                                                        DBU in amyl alcohol                                         I-70     Cu        Reaction of CuCl, the                                                                          720                                                            intermediate (V-49) and                                                        DBU in amyl alcohol                                         I-71     Co        Reaction of CoCl.sub.2, the                                                                    735                                                            intermediate (V-50) and                                                        DBU in amyl alcohol                                         I-72     Co        Reaction of CoCl.sub.2, the                                                                    749                                                            intermediate (V-51) and                                                        DBU in amyl alcohol                                         I-73     Mn        Reaction of MnCl.sub.2, the                                                                    723                                                            intermediate (V-52) and                                                        DBU in amyl alcohol                                         I-74     Fe        Reaction of FeCl.sub.2, the                                                                    730                                                            intermediate (V-53) and                                                        DBU in chloronaphthalene                                    I-75     Cu        Reaction of CuCl, the                                                                          750                                                            intermediate (V-54) and                                                        DBU in chloronaphthalene                                    I-76     Cu        Reaction of CuCl, the                                                                          716                                                            intermediate (V-55) and                                                        DBU in chloronaphthalene                                    I-77     Cu        Reaction of CuCl, the                                                                          755                                                            intermediate (V-56) and                                                        DBU in chloronaphthalene                                    I-78     Fe        Reaction of FeCl.sub.2, the                                                                    758                                                            intermediate (V-57) and                                                        DBU in chloronaphthalene                                    I-79     Zn        Reaction of Zn(OAc).sub.2, the                                                                 700                                                            intermediate (V-58) and                                                        DBU in chloronaphthalene                                    I-80     VO        Reaction of VO(acac).sub.2, the                                                                729                                                            intermediate (V-59) and                                                        DBU in chloronaphthalene                                    I-81     VO        Reaction of VO(acac).sub.2, the                                                                728                                                            intermediate (V-60) and                                                        DBU in chloronaphthalene                                    I-82     VO        Reaction of VO(acac).sub.2, the                                                                720                                                            intermediate (V-61) and                                                        DBU in amyl alcohol                                         I-83     Pd        Reaction of PdCl.sub.2, the                                                                    745                                                            intermediate (V-62) and                                                        DBU in amyl alcohol                                         I-84     Fe        Reaction of FeCl.sub.2, the                                                                    755                                                            intermediate (V-63) and                                                        DBU in amyl alcohol                                         I-85     Cu        Reaction of CuCl, the                                                                          765                                                            intermediate (V-64) and                                                        DBU in amyl alcohol                                         I-86     Cu        Reaction of CuCl, the                                                                          745                                                            intermediate (V-65) and                                                        DBU in amyl alcohol                                         I-87     Cu        Reaction of CuCl, the                                                                          695                                                            intermediate (V-66) and                                                        DBU in chloronaphthalene                                    I-88     Fe        Reaction of FeCl.sub.2, the                                                                    750                                                            intermediate (V-67) and                                                        DBU in amyl alcohol                                         I-89     Fe        Reaction of FeCl.sub.2, the                                                                    777                                                            intermediate (V-68) and                                                        DBU in amyl alcohol                                         I-90     Co        Reaction of CoCl.sub.2, the                                                                    790                                                            intermediate (V-69) and                                                        DBU in amyl alcohol                                         I-91     Pd        Reaction of PdCl.sub.2, the                                                                    703                                                            intermediate (V-70) and                                                        DBU in amyl alcohol                                         I-92     Ni        Reaction of NiCl.sub.2, the                                                                    705                                                            intermediate (V-71) and                                                        DBU in amyl alcohol                                         I-93     GeCl.sub.2                                                                               Reaction of GeCl.sub.4, the                                                                    750                                                            intermediate (V-72) and                                                        DBU in amyl alcohol                                         I-94     Zn        Reaction of Zn(OAc).sub.2, the                                                                 758                                                            intermediate (V-73) and                                                        DBU in amyl alcohol                                         I-95     Zn        Reaction of Zn(OAc).sub.2, the                                                                 735                                                            intermediate (V-74) and                                                        DBU in amyl alcohol                                         I-96     Pb        Reaction of Pb(OAc).sub.2, the                                                                 765                                                            intermediate (V-75) and                                                        DBU in amyl alcohol                                         I-97     Zn        Reaction of Zn(OAc).sub.2, the                                                                 715                                                            intermediate (V-76) and                                                        DBU in amyl alcohol                                         I-98     Cu        Reaction of CuCl, the                                                                          716                                                            intermediate (V-77) and                                                        DBU in amyl alcohol                                         I-99     Ni        Reaction of NiCl.sub.2, the                                                                    716                                                            intermediate (V-78) and                                                        DBU in amyl alcohol                                         I-100    Ni        Reaction of NiCl.sub.2, the                                                                    751                                                            intermediate (V-79) and                                                        DBU in amyl alcohol                                         I-101    Fe        Reaction of FeCl.sub.2, the                                                                    725                                                            intermediate (V-80) and                                                        DBU in amyl alcohol                                         I-102    Cu        Reaction of CuCl, the                                                                          724                                                            intermediate (V-81) and                                                        DBU in amyl alcohol                                         I-103    Zn        Reaction of Zn(OAc).sub.2, the                                                                 715                                                            intermediate (V-82) and                                                        DBU in amyl alcohol                                         I-104    Pd        Reaction of PdCl.sub.2, the                                                                    708                                                            intermediate (V-83) and                                                        DBU in chloronaphthalene                                    I-105    Pd        Reaction of PdCl.sub.2, the                                                                    713                                                            intermediate (V-84) and                                                        DBU in chloronaphthalene                                    I-106    Zn        Reaction of Zn(OAc).sub.2, the                                                                 750                                                            intermediate (V-85) and                                                        DBU in chloronaphthalene                                    I-107    SiCl.sub.2                                                                               Reaction of SiCl.sub.4, the                                                                    715                                                            intermediate (V-86) and                                                        DBU in chloronaphthalene                                    I-108    Fe        Reaction of FeCl.sub.2, the                                                                    717                                                            intermediate (V-87) and                                                        DBU in chloronaphthalene                                    I-109    Co        Reaction of CoCl.sub.2, the                                                                    719                                                            intermediate (V-88) and                                                        DBU in chloronaphthalene                                    I-110    Cu        Reaction of CuCl, the                                                                          715                                                            intermediate (V-89) and                                                        DBU in chloronaphthalene                                    I-111    Pd        Reaction of PdCl.sub.2, the                                                                    752                                                            intermediate (V-90) and                                                        DBU in chloronaphthalene                                    I-112    Pb        Reaction of Pb(OAc).sub.2, the                                                                 725                                                            intermediate (V-91) and                                                        DBU in chloronaphthalene                                    I-113    Cu        Reaction of CuCl, the                                                                          685                                                            intermediate (V-92) and                                                        DBU in chloronaphthalene                                    I-114    Cu        Reaction of CuCl, the                                                                          686                                                            intermediate (V-93) and                                                        DBU in chloronaphthalene                                    I-115    Fe        Reaction of FeCl.sub.2, the                                                                    694                                                            intermediate (V-94) and                                                        DBU in chloronaphthalene                                    I-116    Fe        Reaction of FeCl.sub.2, the                                                                    692                                                            intermediate (V-95) and                                                        DBU in chloronaphthalene                                    I-117    Fe        Reaction of FeCl.sub.2, the                                                                    682                                                            intermediate (V-96) and                                                        DBU in amyl alcohol                                         I-118    Cu        Reaction of CuCl, the                                                                          686                                                            intermediate (V-97) and                                                        DBU in amyl alcohol                                         I-119    Cu        Reaction of CuCl, the                                                                          679                                                            intermediate (V-98) and                                                        DBU in amyl alcohol                                         I-120    Co        Reaction of CoCl.sub.2, the                                                                    689                                                            intermediate (V-99) and                                                        DBU in chloronaphthalene                                    I-121    Cu        Reaction of CuCl, the                                                                          705                                                            intermediate (V-100) and                                                       DBU in amyl alcohol                                         I-122    Co        Reaction of CoCl.sub.2, the                                                                    715                                                            intermediate (V-101) and                                                       DBU in amyl alcohol                                         I-123    Cu        Reaction of CuCl, the                                                                          785                                                            intermediate (V-102) and                                                       DBU in amyl alcohol                                         I-124    Pb        Reaction of Pb(OAc).sub.2, the                                                                 718                                                            intermediate (V-103) and                                                       DBU in amyl alcohol                                         ______________________________________                                     

What is claimed is:
 1. An optical recording medium comprising a substrate and a recording layer which comprises a phthalocyanine compound represented by the following formula III: ##STR344## wherein R²², R²⁵, R²⁶, R²⁹, R³⁰, R³³, R³⁴ and R³⁷ independently represent a group represented by the below-described formula (IV) or a hydrogen or halogen atom with the proviso that, in each of the combinations of R²² and R²⁵, R²⁶ and R²⁹, R³⁰ and R³³, and R³⁴ and R³⁷, at least one of the groups is represented by the formula (IV); R²³, R²⁴, R²⁷, R²⁸, R³¹, R³², R³⁵ and R³⁶ independently represent an unsubstituted C₁₋₂₀ alkyl group, a C₁₋₂₀ alkyl group substituted by an alkyl group, an alkoxy group, a halogen atom or a hydroxyl group, an unsubstituted C₁₋₂₀ alkoxy group, a C₁₋₂₀ alkoxy group substituted by an alkyl group, an alkoxy group, a halogen atom or a hydroxyl group, an unsubstituted C₁₋₂₀ alkylamino group, a C₁₋₂₀ alkylamino group substituted by an alkoxy group, a halogen atom or a hydroxy group, an unsubstituted C₂₋₂₀ dialkylamino group, a C₂₋₂₀ dialkylamino group substituted by an alkoxy group, a halogen atom or a hydroxy group, an unsubstituted phenoxy group, a phenoxy group substituted by at least one member of the group consisting of C₁₋₅ alkyl groups, C₁₋₃ alkoxy groups and halogen atoms, an unsubstituted phenylthio group, a phenylthio group substituted by at least one member of the group consisting of C₁₋₅ alkyl groups, C₁₋₃ alkoxy groups and halogen atoms, --COOR³⁸ in which R³⁸ is a hydrogen atom, an unsubstituted C₁₋₂₀ alkyl group, a C₁₋₂₀ alkyl group substituted by an alkoxy group, a halogen atom or a hydroxy group, hydroxy or mercapto group or a halogen or hydrogen atom; and Met represents a metal atom; Formula (IV) being ##STR345## wherein X² and Z² represent an oxygen or sulfur atom, R³⁹, R⁴⁰ and R⁴¹ independently represent a hydrogen atom, an unsubstituted C₁₋₂₀ alkyl group, or a C₁₋₂₀ alkyl group substituted by an alkyl group, an alkoxy group, a halogen atom or a hydroxy group, p², q², u², m² and t² are 1, r² =0, 1² and n² are 0-10, ##STR346## B² is --U⁵ --(CH₂)_(c) --, --V⁵ -- CH(CH₃ CH₂ !-- or --W⁵ -- CH₂ CH(CH₃)!--, U⁵, V⁵ and W⁵ independently representing an oxygen or sulfur atom and c being an integer of 1-3, and D² is --C(R⁴²)H--, R⁴² representing a hydrogen atom or a substituted or unsubstituted alkyl group. 